CN1824606A - Copper replenishing agent for controlled and slow-release copper, preparation method and application - Google Patents

Abstract

The present invention discloses a controlled slowly-released copper-supplementing preparation, its preparation method and application. It is a zeolite containing active copper, the copper content in the zeolite is 1.5-10 wt%. Its preparation method uses copper salt and natural or synthetic zeolite as raw material and makes them undergo the following steps: adsorption, ion exchange reaction, filtration, drying and pulverization so as to obtain the invented zeolite containing active copper. It can be used as animal feed additive, also can be used for preparing human oral health-care product and medicine for supplementing copper.

Description

Copper replenishing agent for controlled and slow-release copper, preparation method and application

technical field

The invention relates to a controlled and slow-release copper supplementation agent for copper, a preparation method and application.

Background technique

Copper is one of the essential trace elements for humans and animals. As a general essential nutrient element, pigs and chickens require 3-8 mg/kg of copper (NRC, 1994; 1998). The uniqueness of the trace element copper to livestock and poultry lies in the growth-promoting effect of adding high doses of copper (usually in the form of copper sulfate). At present, although the growth-promoting mechanism of high copper is not clear, high-dose copper has been widely used in animal husbandry as an efficient and cheap growth-promoting additive. At present, the most commonly used copper source at home and abroad is copper sulfate, but the production and use of copper sulfate can cause the following problems: (1) The compatibility between copper sulfate and other ingredients in the feed is poor, and it can oxidize and destroy some nutrients in the feed, such as vitamins , grease or fat, etc., reducing the palatability and nutritional value of the feed; (2) Copper sulfate is irritating to the gastrointestinal mucosa, and long-term addition of copper at the level of pharmacological effects will cause toxicity and side effects to the body; (3) Modern nutritional formula In order to reduce the antagonism of copper to other essential mineral elements, the addition of zinc and iron in the diet is often increased accordingly, and a large amount of metal elements are discharged into the environment with the feces, resulting in waste of resources and environmental pollution. In order to seek a high-efficiency copper source that can not only promote the growth of livestock and poultry, but also increase the bioavailability of copper and reduce the dosage of copper, many scholars have studied different types of copper sources such as copper citrate, copper lysine, and copper methionine in recent years. A lot of beneficial research work has been done on copper amino acid chelate, copper proteinate, etc., but the current literature reports show that it is not yet certain that this type of organic copper source can be used as an efficient copper source for animals. Therefore, the development and application of new copper sources with high efficiency absorption and utilization in animal husbandry production to maximize the growth-promoting effect of copper and reduce the environmental pollution caused by copper discharge is arousing great interest and widespread concern of researchers.

As an essential trace element, copper also has many important physiological functions in human nutrition. Copper is a component of many metalloenzymes. As a trace element necessary for the synthesis of collagen and elastin, copper plays an important role in the repair of fractures; at the same time, copper is a component of many antioxidant enzymes, such as ceruloplasmin , copper zinc superoxide dismutase, etc., may also play an active role in promoting blood circulation, removing stasis, and reducing inflammation. Copper is required for normal bone metabolism. Many studies have shown that osteoblast activity decreases in copper-deficient animals; one of the main manifestations of clinical copper deficiency is abnormal bone development.

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 copper supplement, its preparation method and application, specifically a zeolite containing active copper, its preparation method and application.

The controlled and slow-release copper copper supplement of the present invention is a zeolite containing active copper prepared by adopting copper salt and natural or synthetic zeolite through adsorption and ion exchange reaction. The content is 1.5 to 10%.

The preparation method of the copper replenishing agent of controlled and slow-release copper 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 copper salt with a copper 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 copper 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.

The said copper salt of the present invention is inorganic copper salt or organic copper salt, and inorganic copper salt can be copper chloride, copper nitrate or copper sulfate, and organic copper salt can be copper acetate, glycine copper, copper citrate, copper gluconate, Copper lactate, copper lysine, or copper 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 controlled and slow-release copper supplementation agent for copper 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 copper supplement is used as feed additive for livestock, poultry, aquatic animals, cattle and sheep.

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

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 copper It has a controlled and slow-release effect, thereby greatly improving the absorption and utilization rate of copper.

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

(3) The copper supplement prepared by the present invention can be used as a feed additive to supplement copper in livestock, poultry, aquatic animals, cattle, sheep, etc.; Health products and medicines for human diseases have a wide range of applications.

(4) The copper-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 copper acetate with a copper 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-release copper supplement, and the content of copper in the zeolite was 2% by weight percentage.

96 piglets with a body weight of 7.8kg were divided into 4 groups according to the requirements of the feeding experiment. Each group had 3 replicates, and each replicate had 8 pigs (half male and half female). The control group was fed a basal diet (5 mg/kg Cu, added in the form of CuSO ₄ ), and the test group was fed a basal diet supplemented with 240 mg/kg copper sulfate and 5 mg/kg, 60 mg/kg controlled slow-release copper, respectively. The test pigs were fully fed (feeding four times a day) and had free access to water for 45 days. At the later stage of the feeding experiment, 6 test pigs were selected from each group, a total of 24, and the digestion test was carried out with Cr ₂ O ₃ as the exogenous indicator. After the feeding experiment, according to the requirements of similar body weight, 6 test pigs (half male and female) were selected from each group, a total of 24 pigs were slaughtered according to conventional methods, and samples were collected.

Feeding experiments showed that: compared with the control group (adding 5 mg/kg copper sulfate), adding 5 mg/kg and 60 mg/kg controlled slow-release copper increased the daily gain of piglets by 6.5% (P<0.1) and 15.4% ( P＜0.01), the ratio of material to weight decreased by 7.2% (P＜0.05) and 15.8% (P＜0.01) respectively, and the frequency of diarrhea decreased by 42.1% (P＞0.05) and 75.2% (P＜0.05); add 240mg /kg copper sulfate had no significant effect on the daily gain of piglets, but increased the diarrhea rate of piglets by 92.5% (P<0.01). The results of the digestion test showed that the addition of 60mg/kg controlled-release copper increased the apparent digestibility of feed crude protein, crude fat and calcium by 7.6% (P<0.05), 87.5% (P<0.05) and 75.4% ( P<0.05). The determination of copper-containing enzyme activity revealed that adding 240mg/kg copper sulfate and 5mg/kg, 60mg/kg controlled slow-release copper made the SOD activity in the liver increase by 125.4% ((P<0.05) and 135.4% (P<0.05) respectively. ), 248.5% (P<0.01). Adding 5mg/kg and 60mg/kg controlled slow-release copper increases serum growth hormone concentration by 85.2% (P<0.05) and 101.2% (P<0.05) respectively compared with the control group.

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 copper chloride with a copper 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 3) was dried and crushed to 300 meshes to obtain a controlled-release copper supplement, and the content of copper in the zeolite was 5% by weight percentage.

Effects of controlled and slow-release copper on growth and endocrine of broiler chickens:

The effect of controlled and slow-release copper on the growth and endocrine of broiler chickens was studied by taking AA commercial mixed chicks as the test object. Select 240 broiler chickens at the age of 1 day with similar body weights, and randomly divide them into 3 groups (each group has 4 repetitions, and each repetition has 20 feathers), which are respectively blank control, 20mg/kg copper methionine and 20mg/kg controlled slow-release type copper. Under the conditions of free access to food, water and 24-hour light, a 56-day feeding experiment was carried out. After the feeding test, 16 test chickens (half male and half female) of similar body weight were selected for each group, a total of 48 chickens were given water and no feed, fasted for 12 hours, slaughtered, and serum samples were taken.

The feeding test results showed that: compared with the control group, adding controlled-release copper and copper methionine increased the daily gain by 8.7% (P<0.05) and 5.2% (P>0.05); The weight ratio decreased by 7.8% (P<0.05); while copper methionine had no significant effect on the material weight ratio.

Copper methionine and controlled-release copper increased serum _T4 activity by 35.6% (P<0.05) and 81.2% (P<0.01), respectively. Controlled-release copper increased the levels of insulin and insulin-like growth factor I by 24.7% (P<0.05) and 45.6% (P<0.01), respectively.

The results of this study suggest that the effect of controlled and slow-release copper on improving the growth of broilers is slightly better than that of the same dose of copper methionine.

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 copper nitrate with a copper 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-release copper supplement. The content of copper in MCM-41 was 10% by weight percentage.

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

One-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 copper compound (analytical pure CuSO ₄ .5H ₂ O), controlled slow Released copper and commercially available yeast copper. There were 4 levels for each treatment, copper additions were 0, 10, 20, 30 mg/kg, and 4 replicates were set for each level. Each repetition occupies a brooding cage made of non-copper-plated material, and 4 chickens are raised. Male and female are half and half. 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 content of copper in tibial ash was measured by atomic absorption spectrophotometry.

Relative biological values were calculated using the slope ratio method. Taking the analytically pure CuSO ₄ .5H ₂ O as the reference standard, calculate the regression slope of other copper sources when the slope of the regression line is 100. This is assuming that the biological value of the analytically pure CuSO ₄ .5H ₂ O of the reference standard is 100, the relative biological value of other copper sources, the results are shown in Table 1.

Table 1 Relative biological value of different copper sources Indicator processing CuSO ₄ .5H ₂ O Controlled Release Copper yeast copper Daily gain Tibial ash weight Tibial ash copper content Tibial copper deposition 100100100100 195350125230 187315158205

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 copper citrate with a copper 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) was dried and crushed to 500 meshes to obtain a controlled-release copper supplement. The content of copper in the zeolite was 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 copper lysine with a copper 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 copper supplement. The content of copper 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 copper gluconate with a copper 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 copper supplement, and the content of copper in the zeolite was 4% by weight percentage.

The controlled and slow-release copper supplementation agent is used as a copper supplementation feed additive for livestock, poultry, aquatic animals, cattle, and sheep. 5~60mg/kg, chicken 5~20mg/kg, duck 5~20mg/kg, fish 3~30mg/kg, soft-shelled turtle 3~10mg/kg, shrimp 3~10mg/kg.

Controlled and slow-release copper supplements are used to prepare human oral copper supplements and health care products and medicines for treating human diseases by administering therapeutic copper. Take 1-2 times a day, and the daily dose should not exceed 2-2 times. 8mg is appropriate.

Claims (9)

1. the supplement copper agent of a controlled release type copper, it is characterized in that it is to adopt mantoquita and a kind of zeolite that contains active copper natural or that the artificial synthetic zeolite is prepared from through absorption, ion exchange reaction, by weight percentage, the content of copper in zeolite is 1.5～10%.

2. the supplement copper agent of a kind of controlled release type copper according to claim 1 is characterized in that described mantoquita is inorganic mantoquita or organic copper salt.

3. the supplement copper agent of a kind of controlled release type copper according to claim 2, it is characterized in that described inorganic mantoquita is cupric chloride, cupric nitrate or copper sulfate, organic copper salt is neutralized verdigris, glycocoll-copper, Cuprocitrol, copper gluconate, cupric lactate, Copper lysinate or copper methionine.

4. the preparation method of the supplement copper agent of a controlled release type copper as claimed in claim 1 is characterized in that the step of method is as follows:

1) zeolite is ground to greater than 300 orders, adds water and stir, make concentration and be 1%～10% suspension slurry;

2) with copper content be the mantoquita of zeolite weight 1.5～10%, slowly add in the suspension slurry of step 1) that the pH value that detects and regulate ore pulp is 3.0～6.5, room temperature reaction 4～10 hours in stirring down;

3) detection step 2) the pH value of slurries is regulated with basic solution, and making slurry pH value is 7.0～8.5; Wash 2～5 times, filter or centrifuge dehydration;

4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the controlled release type supplement copper agent.

5. the preparation method of the supplement copper agent of a kind of controlled release type copper according to claim 4 is characterized in that described mantoquita is inorganic mantoquita or organic copper salt.

6. the preparation method of the supplement copper agent of a kind of controlled release type copper according to claim 5, it is characterized in that described inorganic mantoquita is cupric chloride, cupric nitrate or copper sulfate, organic copper salt is neutralized verdigris, glycocoll-copper, Cuprocitrol, copper gluconate, cupric lactate, Copper lysinate or copper methionine.

7. the preparation method of the supplement copper agent of a kind of controlled release type copper according to claim 4 is characterized in that described basic solution is that concentration is the aqueous solution of sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate or the saleratus of 0.5～10moL/L.

8, a kind of purposes of supplement copper agent of controlled release type copper as claimed in claim 1 is characterized in that it is used as livestock and poultry, aquatic animal, ox, sheep benefit copper feed additive.

9. the purposes of the supplement copper agent of a controlled release type copper as claimed in claim 1 is characterized in that it is used as healthcare products and the medicine for preparing human oral benefit copper and treat human diseases by the copper of drug treatment.