CN100364548C - Controlled and slow-release iron iron supplement and its preparation method and application - Google Patents

Abstract

The invention discloses an iron supplement of controlled and slow-release iron, a preparation method and application thereof. It is a zeolite containing active iron, and the content of iron in the zeolite is 1.5-10% by weight. The preparation method is to adopt the adsorption and ion exchange reaction of divalent iron salt and natural or artificially synthesized zeolite, and then filter, dry and pulverize to prepare the zeolite containing active iron. The method has simple technological process, low production cost and is easy to popularize and implement. Because the carrier zeolite has good biocompatibility and gastrointestinal mucosa affinity, regular interconnected pore structure and cage space, high surface activity and huge specific surface area, it has the ability to control the loading of iron. Release, thus greatly improving the absorption and utilization of iron. The controlled and slow-release iron prepared by the present invention can be used as a feed additive for iron supplementation of livestock, poultry, aquatic animals, cattle, sheep, etc.; it can also be used to prepare human oral iron supplementation and treat human beings by administering therapeutic iron Health care products and medicines for diseases have a wide range of applications.

Description

Controlled and slow-release iron iron supplement and its preparation method and application

technical field

The invention relates to an iron supplement of controlled and sustained release type iron, a preparation method and application thereof.

Background technique

Iron is an essential trace element for animals. It is an essential component of hemoglobin and myoglobin. The activity of oxidase is closely related. Iron participates in the normal transport of oxygen in body tissues, directly affects the energy and protein metabolism of the body, and also affects the immune function and reproductive performance of animals. The iron content in conventional feed is relatively high, and in terms of quantity alone, it can already meet the needs of animals. However, the utilization rate of iron in plant feed is extremely low, and the degree of intensification of the breeding industry is getting higher and higher. The efforts in both breeding and nutrition have greatly increased the growth rate of livestock and poultry. Therefore, some iron must be artificially added to meet the needs of livestock and poultry. Artificially added are called iron additives. So far, the development of iron additives has gone through three stages, correspondingly there are three generations of products. The first generation product is inorganic iron: ferrous sulfate, ferrous carbonate, ferric oxide, ferric chloride, ferrous chloride, etc.; the second generation product is organic iron salt: ferric lactate, ferric fumarate, ferrous citrate Iron, iron fumarate, etc.; the third generation is protein source or amino acid chelated iron: methionine chelated iron, threonine chelated iron, glycine iron, etc.

Iron deficiency or iron deficiency anemia occurs when there is iron deficiency or poor iron utilization in the human body, especially for children over 4 months, and women who are pregnant, breast-feeding, or menstruating. The iron fortifiers approved for use in my country mainly include ferrous sulfate, ferric citrate, ferric ammonium citrate, ferric ammonium fumarate, ferrous gluconate, and ferrous lactate. The evaluation of the quality of iron fortifiers for food mainly depends on their performance, which generally includes the following two aspects: one is to look at their relative bioavailability, and the other is to look at whether they change the color or taste of food after adding them. Relative bioavailability is closely related to the solubility of iron fortifiers. Generally, those that are easily transformed into Fe ²⁺ ions in the stomach are easily absorbed. However, judging from the currently used iron fortifiers, those with good solubility and high bioavailability are often more likely to change the color and taste of food. Moreover, iron supplements such as ferrous sulfate and ferrous gluconate are often accompanied by side effects such as gastrointestinal irritation and rusty smell, and iron (II) can generate endogenous free radicals in the body, leading to cell membrane damage caused by cell membrane lipid peroxidation. Therefore, researchers from various countries have been searching for iron nutritional fortifiers with few side effects and high bioavailability for many years.

The controlled and sustained release system is selective and controllable to the release site, speed and mode of drugs, pesticides, fertilizers and spices, which can realize the targeted delivery and controlled and sustained release of the target substance, improve its utilization rate and effect, and control the slow release. The research and application of the interpretation system will bring a new technological revolution to related industries. Controlled release technology also shows great application prospects and theoretical significance in the research and development of feed additives. It can promote the high performance and environmental friendliness of products, and will provide materials and materials for the sustainable development of animal husbandry at a new level. Technical Guarantee.

The key to the controlled release technology is the selection of the controlled release carrier. Zeolite is a kind of naturally occurring or artificially synthesized aluminosilicate with regular pore structure. Its chemical composition is: M _2/n Al ₂ O ₃ x xSiO ₂ yH ₂ O, where M represents metal cations, n is the valence state of the metal cation, x is the ratio of silicon to aluminum, and y is the number of saturated water molecules. The structure of natural zeolite is complex due to different ore-forming conditions, and the structure of artificially synthesized zeolite molecular sieve is simple and controllable. TO ₄ (T=Si, Al or other elements) tetrahedra, the most basic structural unit of molecular sieves, can not only be connected to each other to form four-membered, six-membered and other unit rings through oxygen bridges, but also can be further connected to form double rings. These single and double rings Further connection will form various porous zeolite material skeleton structures such as cage-like or different-dimensional pore systems. For example, the eight-membered oxygen ring system includes erionite, chabazite, and α-zeolite. These zeolites are mesoporous materials, and the pore system contains interconnected supercages; the ten-membered ring system is also called mesoporous zeolite, including natural zeolite and A large number of artificially synthesized high-silica zeolites, their skeleton structures contain five-membered oxygen rings, and most of the channel systems are non-intersecting single channels; the dual-channel system zeolites have twelve-membered and eight-membered oxygen ring openings or ten-membered and eight-membered The internal communication channels of the oxygen element openings, such as clinoptilolite, mordenite, stilbite, etc., this type of zeolite has two pore sizes of mesopores and micropores. Because zeolite has good biocompatibility and gastrointestinal mucosal affinity, regular interconnected pore structure and cage-like space, high surface activity and huge specific surface area, it is very suitable as a controlled and sustained release carrier.

Contents of the invention

The object of the present invention is to provide a controlled and slow-release iron iron supplement and its preparation method and application.

Controlled and slow-release iron iron supplement is a kind of zeolite containing active iron prepared by adopting divalent iron salt and natural or synthetic zeolite through adsorption and ion exchange reaction. The content of iron in zeolite is calculated by weight percentage 1.5-10%.

The preparation method of the iron supplement of controlled and slow-release iron of the present invention comprises the following steps:

1) Grinding the zeolite to a size larger than 300 mesh, adding water and stirring evenly to prepare a suspension slurry with a concentration of 1% to 10%;

2) Slowly add ferrous salt with an iron content of 1.5-10% of the zeolite weight into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 3.0-6.5, and react at room temperature for 4-10 hours ;

3) In the detection step 2) the pH value of the slurry is adjusted with an alkaline solution so that the pH value of the slurry is 7.0-8.5; washed with water for 2-5 times, filtered or centrifugally dehydrated;

4) Drying and crushing the filter cake obtained in step 3) to a size larger than 300 mesh to obtain a controlled and slow-release iron supplement.

Said zeolite in the present invention can be natural or synthetic zeolite. Synthetic zeolites are commercially available or prepared by known preparation methods, and their preparation techniques are well known.

Said ferrous salt of the present invention is inorganic ferrous salt or organic ferrous salt, and inorganic ferrous salt can be ferrous chloride, ferrous nitrate or ferrous sulfate, and organic ferrous salt can be glycine Ferrous, ferrous citrate, ferrous fumarate, ferrous gluconate, ferrous lactate, ferrous lysine, or ferrous methionine. The alkaline solution is an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate with a concentration of 0.5-10 mol/L.

The slurry dehydration process of the preparation method can be adapted to local conditions, and methods such as centrifugation or filtration can be selected for dehydration. The filter cake obtained after dehydration can be dried using conventional drying equipment. The iron supplement of controlled and slow-release iron after drying is in the form of lumps, which can be crushed with conventional crushing equipment until the particle size is greater than 300 mesh.

The controlled and slow-release iron iron supplement is used as an iron supplement feed additive for livestock, poultry, aquatic animals, cattle and sheep.

The controlled and slow-release iron iron supplement is used as a health care product or medicine for preparing human oral iron supplementation and treating human diseases by administering therapeutic iron.

The present invention has the following advantages:

(1) Because the carrier zeolite has good biocompatibility and gastrointestinal mucosal affinity, regular interconnected pore structure and cage-like space, high surface activity and huge specific surface area, it is suitable for the loaded iron It has a controlled and sustained release effect, thereby greatly improving the absorption and utilization rate of iron.

(2) The present invention adopts the adsorption and ion exchange reaction of ferrous salt and natural or synthetic zeolite, and is filtered, dried and pulverized to make zeolite containing active iron. The method has simple technological process, low production cost, and is easy to popularize and implement .

(3) The iron supplement prepared by the present invention can be used as a feed additive for iron supplementation of livestock, poultry, aquatic animals, cattle, sheep, etc.; it can also be used to prepare human oral iron supplementation and to treat Health products or medicines for human diseases, with a wide range of applications.

(4) The iron-supplementing feed additive of the present invention is easy to mix with feed, forms a uniform dispersion system, and is convenient to use.

Detailed ways

The present invention is further illustrated in conjunction with the following examples.

Example 1

1) Grinding the clinoptilolite produced in Jinyun, Zhejiang to 500 mesh, adding water and stirring evenly to make a suspension slurry with a concentration of 10%;

2) Slowly add ferrous chloride having an iron content of 2% by weight of zeolite into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 3.0, and react at room temperature for 4 hours;

3) The pH value of the detection step 2) is adjusted with 0.5moL/L sodium carbonate aqueous solution, so that the pH value of the slurry is 7.0; washed 4 times, filtered and dehydrated;

4) The filter cake obtained in step 3) was dried and crushed to 600 meshes to obtain a controlled and sustained-release iron supplement, and the content of iron in the zeolite was 2% by weight percentage.

Effects of different iron sources on laying performance and egg iron content of laying hens:

Choose 450 chickens of 380-day-old healthy Roman laying hens, and divide them into five groups at random, each group has three repetitions, 90 pigeons in each group, and 30 pigeons in each repetition. One of them is the control group, that is, 80 mg/kg of iron (ferrous sulfate) is added to the basal diet, and the other four groups are the test groups, and 80 mg/kg of iron (iron glycinate) and 160 mg/kg of iron are added to the basal diet respectively. kg (iron glycinate), 600mg/kg (ferrous sulfate), 80mg/kg (controlled release iron). They were reared in three-layer ladder cages with free access to food and water, and the light was 16L+8B. The pre-test period was 1 week, and the main test period was 9 weeks. During the feeding period, the feed intake, number of dead chickens, number of eggs laid, number of broken eggs, total egg weight and average egg weight were recorded. At the end of the feeding experiment, 24 eggs were randomly selected from each group (8 eggs for each repetition), and the iron content in egg yolk was determined.

Feeding test results showed that compared with the control (80mg/kg ferrous sulfate group), the addition of 80mg/kg iron glycinate and controlled slow-release iron made the egg production rate increase by 2.6% (P=0.1) and 4.7% ( P<0.05); 80mg/kg, 160mg/kg iron glycinate and 80mg/kg controlled slow-release iron reduced the egg breaking rate by 38.5% (P<0.05), 34.2% (P<0.05) and 41.3% (P<0.05) respectively <0.05); different iron sources had no significant effect on average egg weight, feed-egg ratio, and culling rate.

The results of egg yolk iron content determination showed that compared with the control group, 80mg/kg iron glycinate, 160mg/kg iron glycinate, 600mg/kg ferrous sulfate, and 80mg/kg controlled slow-release iron increased the iron content in egg yolk by 8.4% ( P>0.05), 35.6% (P<0.01), 41.3% (P<0.01) and 43.2% (P<0.01). It can be seen that 80mg/kg controlled slow-release iron makes the deposition of egg yolk iron reach the effect of 160mg/kg iron glycinate and 600mg/kg ferrous sulfate.

Example 2

1) Grinding a commercially available ZSM-5 zeolite molecular sieve to 300 mesh, adding water and stirring evenly to make a suspension slurry with a concentration of 5%;

2) Slowly add ferrous nitrate with an iron content of 5% by weight of zeolite into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 4.5, and react at room temperature for 6 hours;

3) The pH value of the detection step 2) is adjusted with a 10moL/L aqueous sodium hydroxide solution to make the pH value of the slurry 7.5; washed with water for 3 times, filtered and dehydrated;

4) The filter cake obtained in Step 1 and 3) was dried and crushed to 300 meshes to obtain a controlled-release iron supplement, and the content of iron in the zeolite was 5% by weight percentage.

Effects of different iron sources on growth, metabolism and environment in suckling piglets:

A total of 15 litters of 15 hybrid sows were selected from the same source, the same feeding management conditions, no significant difference in previous reproductive performance, and the third parity, and 15 litters were inseminated with the semen of the same Duroc boar. Du piglets with similar age and no significant difference in birth weight were used as test pigs. Then 5 litters in each group were randomly divided into 3 groups, group I was ferrous sulfate group, group II was iron methionine group, and group III was controlled slow-release iron group. The feeding and management procedures of each group were the same, and the environmental conditions were the same. In the same lactation house, the litters are reared with the sows in a single pen. Both the pig house and the playground are used for natural lactation on the concrete floor, and the lactating sows are fed the same diet. The piglets started to supplement iron with water at the age of 3 days, and each group was given the corresponding iron preparation aqueous solution containing 1000 mg/L of iron, which was dripped on the teats of the sows during lactation (1 mL per teat, twice a day in the morning and evening). The combination of sucking and placing in the water tank for the piglets to drink freely. At the age of 7 days, the feed was started, and at the age of 10 days, the diet was replaced by iron supplementation. The three groups had the same basic diet, added 100mg/kg of different iron preparations, and had free access to food and water. The diet was measured in unlimited amounts by litter, and the experiment ended at 35-day-old weaning.

The results showed that the body weight, daily weight gain, body condition behavior grade, blood hemoglobin value, plasma transferrin content, plasma and liver iron content and other indicators of piglets in groups II and III were all significant at the end of the 35-day test (P<0.05 or P<0.01) was higher than group I; feed consumption, incidence of diarrhea, feces excretion, iron content in feces and iron excretion were significantly (P<0.05 or P<0.01) lower than group I. The 35-day-old body weight, daily weight gain and hemoglobin in group III were also significantly (P<0.05) higher than those in group II, but there was no significant difference in other indicators between group II and group III (P>0.05), indicating that the controlled and sustained-release iron And iron methionine can significantly improve the health status, growth and development, feed remuneration and blood physiological and biochemical indicators of piglets, promote the absorption and utilization of iron in pigs, and reduce the amount of feces and iron excretion in feces. In terms of controlled-release iron and iron methionine, the former has a better iron supplement effect on suckling piglets than the latter, especially in improving piglets' daily weight gain and hemoglobin content (P<0.05).

The pollution of air, water and soil caused by livestock and poultry manure has actually threatened the ecological environment on which we live, and has seriously limited the sustainable development of intensive animal husbandry. In this experiment, the defecation volume, iron content in feces and total amount of excreted iron in group I were significantly (P<0.05) higher than those in group II and group III. The absorption and utilization rate is far lower than the controlled slow-release iron and iron methionine, and because the various ingredients in the diet are mutually restricted and synergistic with each other. An imbalance of any one ingredient has the potential to reduce the absorption and utilization of the other ingredients. This not only wastes resources, increases production costs, but also reduces the effective supply of body nutrients, affects the balance and stability of livestock growth, metabolism and the body's internal environment, and also aggravates environmental pollution due to increased excretion.

Example 3

Preparation: Mesoporous molecular sieve MCM-41 was prepared according to the method of "Modification and Characterization of Mesoporous Molecular Sieve MCM-41 under Mild Conditions" (Zheng Shan, Gao Lian, Guo Jingkun. Journal of Inorganic Materials, 2000, 15(5): 844-848). 41.

1) Grind the mesoporous molecular sieve MCM-41 obtained in the preparatory step to 300 mesh, add water and stir evenly, and make a suspension slurry with a concentration of 1%;

2) Slowly add ferrous glycinate with an iron content of 10% by weight of MCM-41 into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 6.5, and react at room temperature for 10 hours;

3) The pH value of the detection step 2) is adjusted with 5moL/L potassium hydroxide aqueous solution, so that the pH value of the slurry is 8.5; washed 5 times with water, and centrifuged for dehydration;

4) The filter cake obtained in step 3) was dried and crushed to 400 meshes to obtain a controlled and sustained-release iron supplement, and the content of iron in MCM-41 was 10% by weight percentage.

The relative biological value of controlled and slow-release iron to AA broiler chickens:

1-day-old commercial generation AA broiler chickens were designed according to the completely random single factor design method, and three treatments were set up, and the standard iron compound (analytical pure FeSO ₄ .7H ₂ O), control slow Released iron and commercially available iron methionine. There were 5 levels for each treatment, the iron additions were 0, 20, 40, 60, 80 mg/kg, and 3 replicates were set for each level. Each replicate occupies a brooder cage made of non-iron-plated material and houses 4 chickens. Half male and half female. The test period was three weeks, the first week was the pre-test period, and all test chickens were fed with basic diet. The main test period was two weeks, and the rats were fed with the corresponding test diet. At the beginning and end of the main test period, the test chickens were weighed in repetition groups. Calculate average daily gain and feed consumption. At the end of the experiment, in each repetition group, one male and one hen with a body weight similar to that of the group were selected and slaughtered, and the tibia of the right leg was stripped, and the ash weight was measured after merging. Then the iron content in the tibial ash was measured by atomic absorption spectrophotometry.

Relative biological values were calculated using the slope ratio method. Taking the analytical pure FeSO ₄ .7H ₂ O as the reference standard, calculate the regression slope of other iron sources when the slope of the regression line is 100. This is assuming that the biological value of the analytical pure FeSO ₄ .7H ₂ O of the reference standard is 100, the relative biological value of other iron sources, the results are shown in Table 1.

Table 1 Relative biological value of different iron sources

Indicator processing CuSO₄.5H₂O controlled release iron Iron methionine Daily weight gain Tibial ash weight Tibial ash Iron content Tibial iron deposition   100100100100   228320141198 195294125208

Example 4

1) Grinding a commercially available 4A type zeolite molecular sieve to 400 mesh, adding water and stirring evenly to make a suspension slurry with a concentration of 8%;

2) Slowly add ferrous citrate with an iron content of 1.5% by weight of zeolite into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 4.0, and react at room temperature for 6 hours;

3) The pH value of the detection step 2) is adjusted with 2moL/L potassium carbonate aqueous solution, so that the pH value of the slurry is 7.5; washed twice with water, and centrifuged for dehydration;

4) The filter cake obtained in step 3) is dried and crushed to 500 meshes to obtain a controlled and sustained-release iron supplement, and the content of iron in the zeolite is 1.5% by weight percentage.

Example 5

1) Grinding the hematilite produced in Guangxi to 600 mesh, adding water and stirring evenly to make a suspension slurry with a concentration of 4%;

2) Slowly add iron lysine with an iron content of 2.5% by weight of zeolite into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 4.5, and react at room temperature for 10 hours;

3) The pH value of the detection step 2) is adjusted with 6moL/L sodium hydroxide aqueous solution, so that the pH value of the slurry is 7.0; washed 4 times with water, and centrifuged for dehydration;

4) The filter cake obtained in step 3) was dried and crushed to 600 meshes to obtain a controlled-release iron supplement, and the content of iron in the zeolite was 2.5% by weight percentage.

Example 6

Preparation: Prepare ZSM-5 according to the method of "synthesis of ZSM-5 zeolite molecular sieve with high silicon-aluminum ratio and high crystallinity by amine-free method" (Xiang Shouhe, Liu Shuquan, Wang Jingzhong, Li Hexuan, etc. National Invention Patent Authorization No. 1046922C) 5 Zeolite molecular sieves.

1) Grind the ZSM-5 zeolite molecular sieve obtained in the preliminary step to 300 mesh, add water and stir evenly, and make a suspension slurry with a concentration of 6%;

2) Slowly add ferrous fumarate with an iron content of 4% by weight of zeolite into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 4.5, and react at room temperature for 4 hours;

3) The pH value of the detection step 2) is adjusted with 6moL/L potassium hydroxide aqueous solution, so that the pH value of the slurry is 8.0; washed 4 times with water, and centrifuged for dehydration;

4) The filter cake obtained in step 3) was dried and crushed to 400 meshes to obtain a controlled-release iron supplement, and the content of iron in the zeolite was 4% by weight percentage.

Controlled and slow-release iron iron supplements are used as iron supplement feed additives for livestock, poultry, aquatic animals, cattle, and sheep. 40-100mg/kg, broiler 50-80mg/kg, layer 60-100mg/kg, fish 20-80mg/kg, soft-shelled turtle 40-100mg/kg, shrimp 50-100mg/kg.

Controlled and slow-release iron iron supplements are used to prepare human oral iron supplements and health care products and medicines for treating human diseases by administering therapeutic iron. Take 1-2 times a day, and the daily dose is 10-50mg/day. d is appropriate.

Claims (7)

1. An iron supplement of controlled and slow-release iron is characterized in that it is a zeolite containing active iron prepared by adsorption and ion exchange reaction by adopting divalent iron salt and natural or synthetic zeolite. In terms of percentage, the content of iron in the zeolite is 1.5-10%. 2. The iron supplement of controlled and slow-release iron according to claim 1, characterized in that the ferrous salt is an inorganic ferrous salt or an organic ferrous salt. 3. The iron supplement of a kind of controlled and slow-release type iron according to claim 2, it is characterized in that described inorganic divalent iron salt is ferrous chloride, ferrous nitrate or ferrous sulfate, organic divalent iron The salt is ferrous glycinate, ferrous citrate, ferrous fumarate, ferrous gluconate, ferrous lactate, ferrous lysinate or ferrous methionine. 4. A preparation method of an iron supplement of controlled-release iron as claimed in claim 1, characterized in that the steps of the method are as follows: 1) Grinding the zeolite to a size larger than 300 mesh, adding water and stirring evenly to prepare a suspension slurry with a concentration of 1% to 10%; 2) Slowly add ferrous salt with an iron content of 1.5-10% of the zeolite weight into the suspension slurry in step 1) under stirring, detect and adjust the pH value of the slurry to 3.0-6.5, and react at room temperature for 4-10 hours ; 3) In the detection step 2) the pH value of the slurry is adjusted with an alkaline solution so that the pH value of the slurry is 7.0-8.5; washed with water for 2-5 times, filtered or centrifugally dehydrated; 4) Drying and crushing the filter cake obtained in step 3) to a size larger than 300 mesh to obtain a controlled and slow-release iron supplement. 5 . The preparation method of a controlled and slow-release iron iron supplement according to claim 4 , wherein the ferrous salt is an inorganic ferrous salt or an organic ferrous salt. 6 . 6. The preparation method of a kind of controlled and slow-release iron iron supplement according to claim 5, characterized in that said inorganic divalent iron salt is ferrous chloride, ferrous nitrate or ferrous sulfate, organic The divalent iron salt is ferrous glycinate, ferrous citrate, ferrous fumarate, ferrous gluconate, ferrous lactate, ferric lysine or ferrous methionine. 7. The preparation method of a controlled-release iron iron supplement according to claim 4, characterized in that the alkaline solution is sodium hydroxide, potassium hydroxide, Aqueous solutions of sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.