DE102004039486A1 - Production of organic compounds of trace elements, e.g. zinc methionate for use as animal feed additive, involves the solid-state reaction of a metal oxide and a solid organic acid in a pulveriser, e.g. a vibration grinding mill - Google Patents

Abstract

A method for the production of organic compounds of trace elements involves subjecting any dry mixture of an inorganic metal oxide and a solid organic acid to impact and pressure in a pulveriser so that the enthalpy released induces a solid-state reaction to form a metal salt-like compound.

Description

the Use of organic trace element compounds as an additive in the animal nutrition is due to the higher bioavailability currently a special one compared to inorganic compounds Importance attached (H. Schenkel, use of organic trace element compounds to Supply of farm animals, State Institute for Agricultural Chemistry, University Hohenheim, 2000). Trace elements have been known for a long time in small quantities ("in Traces ") in the animal, human or plant organism often vital To fulfill functions Recognize that their lack of manifestation of clinical symptoms leads.

Especially Zinc is an essential, essential trace element metal that in humans and animals as a component of enzymes regulatory in the Organism intervenes, e.g. in the carbon dioxide exchange, in stimulating the metabolism of its own electron transport and in the oxidative Phosphorylation in the liver mitochondria (M. Yamaguchi, M. Kura, S. Okada, Biochem. Pharmacol. 1982, 31, 1289-1293). To the deficiency symptoms belong et al Fertility problems (p. Oishi, K. Hiraga, Toxicol. Appl. Pharmacol. 1980, 53, 35-41; S. Oishi, K. Hiraga, Toxicology 1980, 15, 197-202) and disorders during embryonic development Larson, C. Arnander, E. Cecanova, M. Kjellberg, Teratology 1976, 14, 171-184).

Moreover, the antipruritic properties of zinc amino acid complexes (MS Inokuchi, EP 0514553 ; 11/1992), the immunostimulatory effect of zinc (RL Kincaid, BP Chew, JD Cronrath, J. Dairy Sci., 1997, 80, 1381-1388) and radical scavenging properties of zinc methionine (Bagchi, M. Bagchi, SJ Stohs , Gen. Pharmac., 1997, 28, 85-91).

Only in ionically dissolved or in complex-bound form do the trace elements have their effect. As counterion of the metal to use one (or more) organic acid anions, in particular amino acid anions, and thus to include the already administered for supplementation amino acids in the slightly bioavailable complex with is known and now common practice (see KW Ridenour, US 5702718 ; 12/1997 and patents cited therein). Relevant data on the bioavailability of zinc methionine can be found, inter alia, in J. Cao, PR Henry, R. Guo, RA Holwerda, JP Toth, RC Littell, RD Miles, CB Ammermann, J. Anim. Sci. 2000, 78, 2039-2054 and literature cited therein.

The classic production of salts or complex salts organic acids uses wet-chemical methods, such as those already carried out in 1969 Preparation of zinc methionine as feed additive (D.R. Anderson, US Pat. No. 3,463,858), in which also zinc oxide as a cation source can be used, however, which requires the additional use of hydrochloric acid to achieve the required pH of about 3.5. Such methods involve heating the aqueous Suspension or solution the starting materials to at least 60 to 70 ° C. In a similar way were in 1975 also chromium compounds of amino acids produced (M.M. Abdel-Monem, D.R. Anderson, US Pat. No. 3,925,433). Also wet-chemical and partly under rather drastic conditions (heating up to boiling or use of 6.08 N hydrochloric acid) one year later the preparation of 1: 1 zinc / methionine complexes with an additional inorganic or organic anion (M.M. Abdel-Monem, US Pat. No. 3,941,818). Corresponding manganese, iron, cobalt or copper / methionine complexes have also been proposed (M.M. Abdel-Monem, US Pat. No. 3,950,372; Anderson, M.M. Abdel-Monem, U.S. Pat. No. 4,067,994, M.M. Abdel-Monem, U.S. Pat. Nos. 4,670,269 and 4,678,854, M.M. Abdel-Monem, Anderson, U.S. Pat. No. 4,900,561, D. R. Anderson, U.S. Pat. 4,956,188).

A changed required wet-chemical imaging of zinc / methionine complexes additionally combining the previously generated 30-fold aqueous solutions Acetone to the desired Product (M.M. Abdel-Monem, US Pat. No. 4,021,569). A modern, industrial-scale applied method for the preparation of amino acid-metal complexes, including Zinc Methionine, in the "1.010 pound batch "scale uses (about 3%) ferric sulfate as a catalyst and thus achieves 90% Product yield as well as an increased solubility of the complex (M.D. Anderson, D.R. Anderson, US Pat. No. 4,764,633 and M.M. Abdel-Monem, D.R. Anderson, U.S. Pat. No. 5,430,164). however This process also works wet-chemically with downstream Spray drying. Attempts, at least this energetically demanding drying step, in addition to the already high energy consumption due to heating, to circumvent led to the development, the amino acid-metal complexes undried, i. in solution as a feed supplement to use. Obviously no decisive advantage in the Preparation of said metal salts or complex salts brings the Use of ion exchange resins for the transfer of the heavy metal cation or the respective acid anion (J.-D. Federlin, FR2718132), since these are expensive and regenerated Need to become.

Another methanol-consuming, time-consuming and costly production process (use of sodium methoxide) dates back to 1992. The dropwise combination of Natriummethanolatlösungen with Zinkacetatdihydrat succeeds in the recovery of hydrous zinc bismethionate. However, filtration, washing and subsequent drying of the product are necessary (MS Inokuchi et al., EP0514553 ).

The production methods mentioned generally have the disadvantage that a wet reaction takes place, the subsequent process steps, such as Filter, wash and dry, required. Add to that the use of reagents for pH adjustment possibly the use of iron salts as a catalyst and increased temperatures for influencing the reaction kinetics.

in the Framework of studies on the conversion in particular environmentally hazardous Substances by dry milling was also the sodium salt of the tartaric acid by reaction with sodium carbonates (G. Kaupp, M.R. Naimi-Jamal, H. Ren, H. Zoz, Process Chemical and Pharmaceutical Engineering Worldwide 2003, 4, 24). This procedure is so far exclusively on limited the use of sodium carbonates, which are relatively expensive in several process steps must be produced industrially. About that In addition, the known method has the disadvantage that during the Reacting carbon dioxide must be removed without simultaneously to disperse the very finely divided reaction mixture.

task The invention is a simple dry process for the production of zinc, manganese, iron, copper, cobalt or chromium salts organic acids to disposal to provide, is dispensed with the catalytic reagents and that avoids any peripheral process steps. this will achieved by mixing a mixture of zinc, manganese, iron, Copper, cobalt or chromium oxide or hydroxide with a solid organic acid how methion is exposed to mechanical stress in a vibratory mill. The main type of stress in vibrating mills is the impact (J.-J. Jeng, K.-E. Kurrer, E. Gock: VDI Series 3, No. 282). When shock event comes it is released by micro-deformations in a limited range of energy in the form of short-term high point temperatures, the solid-state reactions trigger can. These partial solid-state reactions can as initial reactions for the total sales of the mill be effective mixture. It is a mechanochemical Reaction. The turnover is determined by the invention essential Operating conditions of the vibratory mill and the mixing ratios of the task material. Decisive for triggering the solid-state reactions is an initial reaction that triggers a chain-like sequence reaction.

The mechano-chemical process according to the invention is characterized by high conversions in an equilibrium reaction with high energy efficiency and a very short reaction time. Furthermore, no stabilizers (eg xanthan) or other additives are required (as for example in the granules of an amino acid and a sparingly soluble metal salt after DE 19510274 ). The conversion of the metal oxide and the organic acid to the desired metal complex can be optimized by adjusting the parameters of speed, amplitude, shape, size, material of the grinding media, degree of filling, feed quantity and grinding time. The analysis of the product can take place within a few minutes using characteristic band positions, shapes and intensities in the infrared spectrum (IR). The structural characterization of zinc bismethionate is found in RB Wilson, P. de Meester and DJ Hodgson, Inorg. Chem. 1977, 16, 1498-1502 or M. Rombach, M. Gelinky, H. Vahrenkamp, Inorg. Chim. Acta 2002, 334, 25-33.

IR data and thermal behavior of zinc amino acid complexes are published by J. Liu, Y. Hou, S. Gao, M. Ji, R. Hu, Q. Shi, J. Therm. Anal. Calorim. 1999, 58, 323-330.

The effect of the mechano-chemical solid-state reactions essential to the invention can also be reproducibly detected by X-ray microstructure recordings. The quantitative determination of the reactions can be based on the measurement of the intensity ratio of certain X-ray diffraction lines of the starting mixture (I ₀ ) and the reaction product (I) proposed by R. Fricke (Z. Elektrochemie 1940, 46, 491) for chemically active substances according to the following equation be made:

It means:
λ = wavelength of the X-ray light
ν = observed reflection angle

Serial tests have shown that the measurement method can be simplified by using the direct I / I ₀ instead of the logarithmic intensity ratio.

The mechano-chemical reaction of metal oxides with an organic acid in the stress by vibratory grinding is fol Following 10 examples explained.

Example 1:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using steel balls (∅ 30 mm) as grinding media, 2 moles of ZnO (162.8 g) and 1 mol of methionine (149.2 g) ground together. It is sampled after 4, 5, 6 and 10 min. As from the IR-recording ( 1 ) and X-ray diffraction analysis ( 2 ), almost complete conversion (> 99%) to zinc bismethionate is achieved.

Example 2:

When using the same satellite for a centrifugal tube mill, which is a very large resonant vibration mill (> 150 mm) and operated at a frequency of 250 min ^-1 , the conversion described in Example 1 is also achieved with the same short milling time.

Example 3:

As has already been explained in the description, the vibration grinding is characterized by impact or compressive stress at which accelerations of up to 12 g are achieved. The ball mill used for fine grinding mill rod with rotating reached at about 30 min ^-1 accelerations of max. 1 g. It was examined whether a reaction of ZnO and methionine can be achieved under these conditions. From the IR images and the X-ray diffraction analysis shows that even after a grinding time of 480 min sales can not be achieved.

Example 4:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using zirconia balls (∅ 20 mm) as grinding media, 1 mol of ZnO (81.4 g) and 1 mol of methionine (149.2 g) ground together. Almost complete conversion to zinc bismethionate is achieved.

Example 5:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using steel balls (∅ 30 mm) as grinding media, 1 mol of ZnO (81.4 g) and 1 mol of histidine (155.2 g) ground together. There is almost complete conversion to zinc bishistidinate.

Example 6:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using steel balls (∅ 30 mm) as grinding media, 1 mol of ZnO (81.4 g) and 1 mol of lysine (146.2 g) ground together. Almost complete conversion to zinc bis-lysinate is obtained.

Example 7:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using zirconia balls (∅ 20 mm) as grinding media, 1 mol of ZnO (81.4 g) and 1 mol of taurine (125.1 g) ground together. Almost complete conversion to zinc bisturinate is achieved.

Example 8:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using steel balls (∅ 30 mm) as grinding media, 2 moles of CuO (159.0 g) and 1 mol of aspartic acid (133.1 g) ground together. Almost complete conversion to zinc asparaginate is obtained.

Example 9:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using steel balls (∅ 30 mm) as grinding media, 2 mol of MnO (141.8 g) and 1 mol of malic acid (134.1 g) ground together. Almost complete conversion to manganese malate is obtained.

Example 10:

In the satellite (5000 cm ³ ) of an eccentric vibration mill with a resonant circuit of 12 mm, a frequency of 960 min ^-1 using zirconia spheres (∅ 20 mm) as grinding media are 1.5 moles of Cr (OH) ₃ (151.5 g) and 1 Mole nicotinic acid (123.1 g) with each other. Almost complete conversion to chromicotinate is obtained.

Claims (5)

Process for the preparation of organic trace element compounds, characterized in that any dry mixture of an inorganic metal oxide and a solid organic acid is subjected to a mechanical impact by impact and pressure in a micronizing machine in such a way that the amount of enthalpy released triggers a solid state reaction to a metal salt-like compound. Method according to claim 1, characterized in that that as Feinstzerkleinerungsmaschine a vibratory mill with a resonant circuit diameter between 6 and 150 mm is used. Process according to claims 1 and 2, characterized that it is the inorganic reactants used as reactants Metal oxides or hydroxides of zinc, manganese, iron, cobalt, Copper and chrome are traded. Process according to claims 1 to 3, characterized that as organic acid carboxylic acids, aminocarboxylic acids, hydroxycarboxylic acids and corresponding sulfonic acids be used. Process according to claims 1 to 4, characterized that the milling process is discontinuous and the product with Help a pressure lock is discharged.