WO2017124665A1 - Composite of zinc-calcium sulfate and use in preparation of feed additive - Google Patents

Abstract

Provided is a composite of zinc-calcium sulfate and the use thereof in the preparation of animal feed additives. A zinc sulfate solution is added to a calcium hydroxide solution for reaction to precipitate the solid, so as to obtain the composite of zinc-calcium sulfate. The use of the composite of zinc-calcium sulfate in an animal feed can significantly reduce the use of zinc in animal husbandry, and can reduce production costs, reduce the toxic and side effects of a high level of zinc, and reduce environmental pollution.

Description

Calcium zinc sulfate composite and application thereof in preparing feed additive Technical field:

The invention belongs to the field of inorganic chemistry, and particularly relates to a novel zinc sulphate complex and its application as a feed additive in the feed processing industry, and further as an animal basic nutrient and a growth promoter.

Background technique:

As one of the trace elements necessary for the animal's body, zinc participates in various metabolic reactions in the body and plays an important role in the growth and development of animals. The total zinc content in normal animals is about 30 ppm. The National Research Council (NRC) recommends that the zinc requirement for piglets is 100 ppm, while pigs are highly resistant to zinc and can reach 20 to 30 times the normal requirement. It has been reported that the addition of 3000ppm zinc oxide to the diet can significantly increase the body weight, average daily gain and daily feed intake of weaned stress piglets, reduce the feed-to-weight ratio and post-weaning diarrhea rate, and effectively prevent weaning stress syndrome in piglets. A large number of studies believe that high-dose zinc oxide can promote the rapid regeneration of tongue mucosal taste bud cells, regulate appetite, inhibit the growth of certain harmful bacteria in the intestine and prolong the residence time of food in the digestive tract, and ensure the digestion and absorption of nutrients in the intestine. It reduces the fermentation of large intestine microorganisms and effectively inhibits piglet diarrhea, thereby increasing daily gain. Hill and Cromwell (1996) have shown that high zinc (3000 ppm zinc oxide) diet levels promote piglet growth. With the widespread use of high-zinc diets, people began to pay attention to the toxic side effects of high-dose zinc on the body and environmental pollution. When zinc is excessive, on the one hand, it causes waste of resources, on the other hand, it causes poisoning of the body, and there is also a complex antagonistic effect between zinc and copper and iron. Any change in the content of the diet may affect other elements. Absorption and changes in their interaction properties may even affect the changes in the physical condition of the entire body. High-dose zinc oxide has been banned in the EU since recent years. Although China's weaned pig feed is allowed to use 2250ppm of zinc, this is a convenient way to achieve high-dose zinc oxide equivalent anti-diarrhea effect while ensuring no heavy metal pollution. The new efficient and safe high-dose zinc oxide replacement product is The development of modern animal husbandry.

Summary of the invention:

The object of the present invention is to provide a calcium zinc sulphate complex, which is used as a basic nutrient in the feed processing industry and as an alternative to high-dose zinc preparations and low-dose zinc sulphate for animal breeding to improve animal performance. And health status.

The zinc calcium sulphate complex according to the present invention is obtained by dropwise adding a zinc sulfate solution to a calcium hydroxide solution to obtain a zinc sulphate complex. The obtained zinc calcium sulfate composite contains, in addition to zinc ions and calcium ions, sulfate groups and 1 to 6 crystal water molecules.

Preferably, the zinc sulfate aqueous solution is added dropwise to a saturated aqueous solution of calcium hydroxide, and the solid is precipitated to obtain a zinc calcium sulfate complex.

The obtained zinc calcium sulphate complex was analyzed by a metal element to have a zinc element content of 26.79% to 29.00% and a calcium element content of 12.80% to 14.00%.

In one embodiment, the obtained zinc calcium sulfate complex has a zinc element content of 26.79% to 28.36% and a calcium element content of 12.80% to 13.04%.

In one embodiment, the obtained zinc calcium sulphate complex has a zinc element content of 28.36% and a calcium element content of 13.04%.

The obtained zinc calcium sulphate complex was analyzed by powder X-ray diffraction, and the corresponding powder diffraction characteristic peak position (2θ) was 11.60°±0.2°, 14.73°±0.2°, 20.72°±0.2°, 25.68°±0.2°, 29.10. °±0.2°, 29.71°±0.2°, 31.81°±0.2°, 32.72°±0.2°.

In a technical solution, the powder diffraction X-ray diffraction analysis of the zinc sulphate complex has a corresponding diffraction characteristic peak position (2θ) of 10.03°±0.2°, 11.60°±0.2°, 12.22°±0.2°, 14.73°± 0.2°, 20.72°±0.2°, 21.27°±0.2°, 23.39°±0.2°, 25.68°±0.2°, 28.18°±0.2°, 29.10°±0.2°, 29.71°±0.2°, 31.08°±0.2° 31.81°±0.2°, 32.72°±0.2°, 33.37°±0.2°, 34.48°±0.2°, 35.06°±0.2°, 42.26°±0.2°, 49.27°±0.2°, 58.51°±0.2°.

In another technical solution, the infrared absorption spectrum characteristic absorption peak of the zinc calcium sulphate complex in the potassium bromide is 3610 cm ^-1 , 3552 cm ^-1 , 3490 cm ^-1 , 3410 cm ^-1 , 1621 cm ^-1 , 1152 cm ^-1 , 1093 cm ^-1 , 1008 cm ^-1 , 966 cm ^-1 , 772 cm ^-1 , 660 cm ^-1 .

Any of the embodiments of any of the aspects of the invention may be combined with other embodiments as long as no contradiction occurs between them. Furthermore, in any of the embodiments of any of the aspects of the present invention, any of the technical features may be applied to the technical features in other embodiments as long as there is no contradiction between them.

On the other hand, the present invention will further apply the zinc calcium sulphate complex according to the present invention to animal breeding, as an animal basic nutrient for use in the feed processing industry or as a high dose zinc preparation, especially zinc oxide. Alternatives are used in the feed processing industry or in the replacement of low-dose zinc sulphate for the nutritional health of animals.

The invention finds through experiments that in the normal zinc demand range of animals, that is, about 100 ppm, the zinc calcium sulphate complex (calculated by zinc ion, the same below) can significantly promote the growth of the animal, and in the case of low dose of zinc ions, it is promoted. The growth performance is achieved by the high dose addition of zinc oxide as an additive zinc ion, and the zinc calcium sulfate complex can be used as a feed additive in the feed processing industry.

In one aspect, when the zinc calcium sulphate complex is used as a feed additive, the required dose of zinc calcium sulphate complex is added to the animal diet feed as a low-dose zinc preparation to satisfy the animal basic nutrition within the nutritional requirements of the animal copper. Demand, because the zinc content of the basic feed is only 25 ~ 30ppm can not meet the minimum needs of animals.

On the other hand, the zinc calcium sulphate complex is used as a feed additive for animal breeding, and the low-dose zinc sulphate complex promotes the growth effect of the animal consistent with the use of high-dose zinc oxide.

As a unique "zinc" and "calcium" macromolecular complex, zinc sulphate complex has a slow and long-lasting release of zinc ions in the digestive tract, avoiding excessive zinc ion concentration in the digestive system and causing zinc poisoning. Zinc ions have a bactericidal effect, and the normal flora of the animal's digestive tract can be maintained at a low concentration in the digestive tract to maintain animal health. At the same time, the zinc sulphate complex contains a certain amount of mineral calcium, which also provides calcium for some nutrient requirements during the feed processing.

The animal to which the zinc calcium sulfate complex is applied as a feed additive includes artificially cultured animals such as poultry, livestock or aquatic animals.

The poultry includes chicken, turkey, guinea fowl, duck, goose, pigeon or donkey at various stages of growth.

The poultry includes pigs, cows, sheep, horses, rabbits, dogs, cats or donkeys at various stages of growth.

The aquatic animals include artificially cultured aquatic animals such as shrimp, fish, clams or crabs.

In the present invention, the zinc sulphate complex has an additive amount in the feed in the animal culture of from 1 to 3,000 ppm, preferably from 100 to 1,500 ppm.

The feed is a common animal diet such as a full-price compound feed, a concentrated feed or a premix.

The application of the zinc calcium sulphate complex of the invention in animal feed can reduce the dosage of zinc ions by about 50% to achieve the same production performance, can significantly reduce the application of zinc in the animal husbandry, can reduce the production cost, and reduce the toxicity of high zinc. Side effects and reduced environmental pollution are zinc compounds with unique advantages.

BRIEF DESCRIPTION OF THE DRAWINGS:

1 is a powder X-ray diffraction pattern (XRPD) of the calcium zinc sulfate complex described in Example 1.

2 is a Fourier infrared spectrum (FT-IR) of the zinc calcium sulphate complex described in Example 1.

detailed description:

For the purpose of describing the invention, the examples are set forth below. However, it is to be understood that the invention is not limited to the embodiments, but merely provides a method of practicing the invention.

The source of the test sample involved in the present invention is shown in Table 1.

Table 1: Sources of test samples used in the examples of the present invention

Test sample	specification	Manufacturer
Zinc sulfate calcium complex	98% purity	Guangzhou Yingsai Te Biotechnology Co., Ltd.
Zinc oxide	Feed grade	Shijiazhuang City People's Chemical Co., Ltd.
Zinc sulfate	Feed grade	Zouping Runrun Chemical Co., Ltd.
Zinc hydroxide	99% purity	Shandong West Asia Chemical Industry Co., Ltd.
Calcium hydroxide	96% purity	Shanghai Jiangyan Industrial Co., Ltd.
Calcium Oxide	98% purity	Changzhou Fengshuo Chemical Co., Ltd.

Example 1 Preparation of calcium zinc sulfate complex

At room temperature, 1.61 kg (10 mol, 1.0 eq) of zinc sulfate was dissolved in 3 L of water to form an aqueous solution of zinc sulfate, which was slowly added dropwise to a saturated aqueous solution of 40 L of calcium hydroxide at 0 ° C, and the reaction mixture was stirred at room temperature overnight. The solid was gradually precipitated, suction filtered, and the residue was dried under reduced pressure at 50 ° C to obtain 2.34 kg of product zinc calcium sulfate complex.

Elemental analysis: the content of zinc element in the zinc calcium sulphate complex was 28.36%, and the content of calcium element was 13.04%;

The XRPD pattern of the calcium zinc sulphate complex is as shown in Fig. 1. The corresponding diffraction characteristic peak positions (2θ): 10.03 ° ± 0.2 °, 11.60 ° ± 0.2 °, 12.22 ° ± 0.2 °, 14.73 ° ± 0.2 °, 20.72 ° ±0.2°, 21.27°±0.2°, 23.39°±0.2°, 25.68°±0.2°, 28.18°±0.2°, 29.10°±0.2°, 29.71°±0.2°, 31.08°±0.2°, 31.81°±0.2 °, 32.72 ° ± 0.2 °, 33.37 ° ± 0.2 °, 34.48 ° ± 0.2 °, 35.06 ° ± 0.2 °, 42.26 ° ± 0.2 °, 49.27 ° ± 0.2 °, 58.51 ° ± 0.2 °;

The FT-IR spectrum of the zinc calcium sulphate complex is as shown in Fig. 2. The corresponding characteristic absorption peaks of the infrared absorption spectrum in potassium bromide are 3610 cm ^-1 , 3552 cm ^-1 , 3490 cm ^-1 , 3410 cm ^-1 , 1621 cm ^-1 , 1152 cm ^-1 , 1093 cm ^-1 , 1008 cm ^-1 , 966 cm ^-1 , 772 cm ^-1 , 660 cm ^-1 .

Example 2: Application effect of zinc calcium sulphate complex in piglet feed

1100 heads of 28-day-old average weight 7.65kg of Du Changda ternary miscellaneous meat pigs as shown in Table 2, 11 groups, each group of 100. After adding different types and different doses of zinc preparations to the teaching materials containing no high dose of zinc, the groups were allowed to eat and drink freely. The weight gain, feed remuneration and diarrhea rate of the test pigs in each test group were counted within 10 days. The results are shown in Table 2. As can be seen from Table 2, 100-2250 ppm of the zinc calcium sulphate complex prepared in Example 1 (based on zinc ion, the same below) can significantly reduce the diarrhea rate of the test pig, and the production performance The improvement has a significant dose effect. The 1125 ppm (as zinc ion) zinc sulphate complex can achieve 2250 ppm ZnO (as zinc ion) improvement in the performance of the test pigs. In addition, the 2250 ppm zinc sulphate complex improved significantly better than diarrhea control (2250 ppm) for diarrhea control and performance.

Table 2 Grouping of different types and different doses of zinc preparations for promoting growth of weaned pigs

Example 3: Application effect of zinc calcium sulfate complex in piglets

500 heads of 42-day-old nursery houses and similar weights of Du Changda ternary miscellaneous meat pigs as shown in Table 3:5 Group, 100 heads per group. After adding different doses of zinc compound to the full-price compound feed of piglets without high-dose zinc, the rats were given ad libitum of feeding and drinking water. The weight gain and feed remuneration of the pigs in each test group were counted for 14 days. The results are shown in Table 3. It can be seen from Table 3 that the 75 ppm zinc calcium sulphate complex (as compared with the zinc content, the zinc sulphate complex prepared in Example 1) can significantly increase the daily gain of the test pig. , improve feed compensation, and the improvement of production performance is significantly better than the same dose of zinc sulfate. In addition, the 150 ppm zinc sulphate complex improved the performance of the test pigs significantly better than the same dose of zinc sulphate.

Table 3: Results of growth-promoting effects of different doses of zinc-calcium complex on piglets

Example 4: Application effect of zinc calcium sulfate complex in broiler feed

300 one-day-old fast yellow broilers (mothers) were grouped according to Table 4, with 50 in each group. After adding different doses of zinc calcium sulphate complex in the full-price compound feed of chicken without additional zinc, the rats were allowed to eat and drink freely. The weight gain and feed remuneration of the test chickens in each test group were counted for 21 days. The results are shown in Table 4. As can be seen from Table 4, 30 and 150 ppm of the zinc calcium sulphate complex prepared in Example 1 (based on zinc, the same below) can significantly increase the daily weight gain of the test chicken and improve the material. The meat ratio and the improvement of the production performance have obvious dose effects, while the 150 ppm zinc sulfate has no improvement on the performance of the test broiler.

Table 4: Results of growth-promoting effects of different doses of zinc-calcium sulfate complex on broilers

Example 5: Application of zinc calcium sulfate complex in aquatic materials

(1) Test materials

Test fish: The test fish used was black carp, and the fish species of the year were provided by Dafeng Fish Farm in Huizhou City, Guangdong Province. The healthy and lively, uniform-sized green carp species were used for formal culture experiments after being kept in large cages (4×2×1.5m ³ ) for 4 weeks. The experimental system was a floating small cage (size 1.1×1.1×1.1m ³ ). Each small cage is equipped with an inflatable head that inflates 24 hours a day. Both the small cage and the holding cage are placed in a 3500 m ² pond at the test site. The pond has a water depth of about 1.5 m and the pond water is fully aerated. During the test, 336 hungry 1d herrings were randomly divided into 7 groups, each group consisted of 4 replicates, and 12 fishes were placed in each replicate. After weighing, they were randomly placed in 28 cages and fed different test feeds. .

Test feed: The test feed was prepared according to the formula of Table 5. Different test groups were added with different doses of zinc preparation (calculated as zinc ion) according to Table 6. The feed ingredients used were finely pulverized and then made into a floating bulking material with a particle size of 3 mm through a Jiangsu shepherd expansion unit. The mold temperature was 130 ° C, and 3% soybean oil was sprayed through the spray equipment, and sealed in a cool place for storage.

Table 5: Formula and chemical composition (%wt.) of test blackfish feed

Raw material composition	content(%)	Raw material composition	content(%)
Fish meal	9.0	Soybean oil	3.0
Casing powder	3.0	Phospholipid	9.0
Cardamom	12.0	Gluten	4.0
Dish	12.0	Blood cell powder	2.0
Monosodium glutamate	3.0	Vc-phosphate	0.1
Secondary powder	12.6	Calcium dihydrogen phosphate	1.8
flour	17.0	Choline chloride	0.2
Bentonite	0.70	Multidimensional	0.1
Rice bran	10.0	Micro-mineral premix	0.5

(2) Test method

Trial management: The test was fed by artificial food restriction. The feeding amount was adjusted once a week. The feeding levels of the two groups (according to the initial weight) were identical and fed twice a day (7:30 and 15:00). The trial lasted for 8 weeks. The water quality was monitored regularly during the test. The whole water temperature was 26.88±3.08°C, DO>5.0mgOL ^-1 , pH 7.8, ammonia nitrogen <0.50mgNL ^-1 and nitrite nitrogen <0.05mgNL ^-1 .

Parameter statistics: During the test, after 1 day of feeding, the whole cage fish were weighed as a whole, and the average weight gain (g) and feed-to-meat ratio were calculated. Calculated as follows:

Average weight gain (g) = average final weight - average initial weight;

Meat to meat ratio = food intake / fish body weight gain;

(3) Test results

The results of the growth promoting test of the calcium zinc sulfate composite prepared in Example 1 on the black carp are shown in Table 6. The results show that 30-120ppm zinc sulphate complex (by zinc, the same below) can significantly improve the daily weight gain of the test fish, improve the feed to meat ratio, and has a significant dose effect on the improvement of production performance. The 30ppm zinc sulphate complex can achieve an improvement of the performance of the test fish by 60ppm zinc sulphate.

Table 6: Application effect of different doses of zinc calcium sulphate complex in aquatic materials

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and combinations thereof may be made without departing from the spirit and scope of the invention. Simplification and the like should all be equivalent replacement means, and are included in the protection scope of the present invention.

Claims (15)

1. A zinc calcium sulphate complex characterized by being prepared by adding a zinc sulphate solution to a calcium hydroxide solution to precipitate a solid to obtain a zinc sulphate complex.
2. The zinc calcium sulphate composite according to claim 1, wherein the zinc sulphate aqueous solution is added dropwise to a saturated aqueous solution of calcium hydroxide to precipitate a solid to obtain a zinc sulphate complex.
3. A zinc calcium sulphate complex characterized in that the zinc-zinc sulfate complex has a zinc element content of 26.79% to 29.00% and a calcium element content of 12.80% to 14.00%.
4. The calcium zinc sulphate complex according to claim 3, wherein the zinc element content is 28.36% and the calcium element content is 13.04%.
5. The zinc calcium sulphate complex according to claim 3, wherein the diffraction characteristic peak position (2θ) of the powder X-ray diffraction pattern of the zinc calcium sulphate complex is 11.60°±0.2°, 14.73°±0.2°. , 20.72 ° ± 0.2 °, 25.68 ° ± 0.2 °, 29.10 ° ± 0.2 °, 29.71 ° ± 0.2 °, 31.81 ° ± 0.2 °, 32.72 ° ± 0.2 °.
6. The zinc calcium sulphate complex according to claim 5, wherein the diffraction characteristic peak position (2θ) of the powder X-ray diffraction pattern of the zinc calcium sulphate complex is 10.03°±0.2°, 11.60°±0.2°. , 12.22°±0.2°, 14.73°±0.2°, 20.72°±0.2°, 21.27°±0.2°, 23.39°±0.2°, 25.68°±0.2°, 28.18°±0.2°, 29.10°±0.2°, 29.71 °±0.2°, 31.08°±0.2°, 31.81°±0.2°, 32.72°±0.2°, 33.37°±0.2°, 34.48°±0.2°, 35.06°±0.2°, 42.26°±0.2°, 49.27°± 0.2°, 58.51° ± 0.2°.
7. The zinc calcium sulphate complex according to claim 6, wherein the zinc absorbing calcium sulfate complex has an infrared absorption spectrum characteristic absorption peak in potassium bromide of 3610 cm ^-1 , 3552 cm ^-1 , 3490 cm ^-1 , 3410 cm. ^-1 , 1621 cm ^-1 , 1152 cm ^-1 , 1093 cm ^-1 , 1008 cm ^-1 , 966 cm ^-1 , 772 cm ^-1 , 660 cm ^-1 .
8. Use of the zinc calcium sulphate complex according to any one of claims 1 to 7 for the preparation of an animal feed additive.
9. The use according to claim 8 wherein said animal feed additive is an animal based nutrient.
10. The use according to claim 8 wherein said animal feed additive is an animal growth promoter.
11. The use according to claim 8, characterized in that the application is the use of a calcium zinc sulphate complex as a substitute for high dose zinc oxide or low dose zinc sulphate in animal feed.
12. The use according to claim 8, characterized in that the zinc calcium sulphate complex is used as an animal feed additive, and the amount of the additive in the animal feed is from 1 to 3,000 ppm based on the zinc content.
13. The use according to claim 12, characterized in that the zinc calcium sulphate complex is used as an animal feed additive, and the amount of the additive in the animal feed is from 100 to 1500 ppm based on the zinc content.
14. The use according to claim 8 wherein the animal is a poultry, domestic animal or aquatic animal.
15. The use according to claim 14, wherein said poultry comprises chicken, turkey, guinea fowl, duck, goose, pigeon or cockroach at various stages of growth; said livestock comprises pigs and cattle of various growth stages , sheep, horses, rabbits, dogs, cats or donkeys; the aquatic animals are fish, shrimp or crabs at various stages of growth.

Images