CN1185953C

CN1185953C - Rare earth gluconate coordination compound fish bait additive

Info

Publication number: CN1185953C
Application number: CNB021239096A
Authority: CN
Inventors: 牛春吉; 唐豫顺; 杨魁跃
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2002-07-09
Filing date: 2002-07-09
Publication date: 2005-01-26
Anticipated expiration: 2022-07-09
Also published as: CN1394521A

Abstract

The present invention relates to a rare earth gluconic acid complex fish bait additive which has the chemical formula of Ln (C6 H11 O7) 3, wherein Ln equals to La, Ce, Pr, Nd and Sm. The preparation method of the prevent invention is that rare earth carbonate is added with water to be stirred into a pasty state; gluconic acid is dissolved in water to be made into a saturated solution, then the gluconic acid water solution is added in the rare earth carbonate paste to be stirred at the temperature of 40 to 50 DEG C till no bubbles appear, and the reaction is continued for 30 to 50 minutes so as to be sufficiently completed; afterwards, the product is separated by evaporation concentration, filtered and naturally dried in the air or dried under an infrared lamp to shorten the drying time. The yield of the gluconic acid rare earth complex reaches 92.6 to 94.3%, and the chemical formula is Ln (C6 H11 O7) 3.

Description

Rare earth gluconate complex fish bait additive

Technical Field

The invention belongs to a bait additive, and particularly relates to a rare earth gluconate complex bait additive and a preparation method thereof.

Background

The developed fishery industry provides increasing animal protein for people in China, and must improve the dietary structure of people in China and improve the health level of people. The method has great and profound significance for the prosperity and the development of Chinese nationality and the long-term safety. The key for developing the fish farming industry is high-efficiency fish bait, but the feed industry in China is still laggard at present. The patent literature has reported some results of bait additive research. For example, preservative antioxidants for fish and shrimp feed (application No. 90100533); compound amino acid is used as bait additive (application numbers 89105175 and 91104189); the complex of humic acid, zinc, manganese, copper and iron is used as bait additive (application No. 95110754). However, research and development of rare earth fish bait additives are only in the beginning stage. At present, research on rare earth as a bait additive is not carried out abroad. Chinese scholars have preliminarily observed that the rare earth compound is added into the fishpond to prevent fish diseases. The results of the small-sized fish-farming preliminary experiments using the rare earth compound show that the rare earth compound additive can enhance the disease resistance of fish bodies and improve the survival rate and the yield of the fish. The research in the comprehensive aspect has the following characteristics: (1) rare earth fish bait additives are rarely reported. (2) Only general experimental observation is carried out, and no characteristic patent result is formed. (3) The main raw materials used as bait additives at present are rare earth inorganic salt simple compounds.

Disclosure of Invention

The invention aims to provide a rare earth gluconate complex bait additive which can enhance the disease resistance of fish, improve the survival rate, increase the weight quickly and reduce the bait coefficient.

It is still another object of the present invention to provide a method for preparing the above additive, which is very simple and easy to handle.

To achieve the above objects, the present invention utilizes the growth promoting effect of rare earth elements, which are a group of elements having specific electronic structures and properties. In recent years, in particular, the bio-inorganic chemistry and biology of rare earths have revealed that rare earths have particular biological effects. It has been found that rare earth has obvious growth promoting effect on plant and animal. For example, the rare earth trace element fertilizer can increase the yield of crops such as wheat and corn by about 10 percent, and the quality of agricultural products is obviously improved. The rare earth is used as the bait additive, which can play a role in promoting the growth of the rare earth and promote the growth of fishes, thereby achieving the purposes of increasing the yield and income. Secondly, the rare earth complex is skillfully utilized to improve the bioavailability of the bait additive. The inorganic salt additive has low bioavailability caused by the easy hydrolysis, high toxicity and instability of the metal inorganic salt in fish bodies. The metal complex is resistant to hydrolysis in fish bodies and is easy to be absorbed and utilized by the fish, and the toxicity of the metal can be obviously reduced by forming the complex. In addition, the metal complex has stable chemical property, oxidation resistance, and moisture decomposition resistance, and is easy to store. The characteristics can greatly improve the fish availability of the rare earth complex bait additive. And thirdly, the biological molecules (biological ligands) are used as carriers of rare earth ions with growth promoting effect, so that the bait additive can be directly absorbed and utilized by fish bodies, unnecessary metabolic processes are reduced, and the physical ability of the fish is saved.

The chemical formula of the gluconic acid rare earth complex fish bait additive provided by the invention is as follows:

Ln(C₆H₁₁O₇)₃

in the formula, Ln is La, Ce, Pr, Nd and Sm;

the used raw materials are as follows:

Ln₂(CO₃)₃(purity 99%), Ln ═ La, Ce, Pr, Nd, Sm gluconic acid (chemically pure).

The bait additive provided by the invention has an outstanding effect of promoting fish growth. The bait additive of the invention promotes the fish to have enhanced disease resistance, improved survival rate, fast weight increment and reduced bait coefficient. Thereby increasing the yield by 10-12% and improving the economic benefit by 12-13%. The main characteristics are as follows: (1) has obvious effect of promoting fish growth, and can enhance the disease resistance of fish, increase the survival rate and promote the growth and development of fish. (2) The bait additive has high bioavailability. (3) Is easy to be absorbed by fish body, and can save the consumption of fish body. (4) Stable chemical property, and easy storage, transportation and use. (5) Low cost and high efficiency.

The rare earth gluconate complex bait additive provided by the invention is prepared by directly reacting rare earth carbonate with gluconic acid. The preparation chemical reaction is as follows:

in the formula, Ln is La, Ce, Pr, Nd and Sm;

L＝HOCH₂-CH(OH)-CH(OH)-CH(OH)-CH(OH)-COO^-，(C₆H₁₁O₇). The preparation reaction has no side reaction, so the reaction product is simple. The reaction product only contains H except the target product rare earth gluconate complex₂O and CO₂。CO₂Escape, clearly ensuring the purity of the target product. With CO₂The evolution of bubbles can also serve as an "indicator" of the progress of the reaction, which facilitates the monitoring of the preparation reaction.

The preparation process comprises the following steps: respectively weighing rare earth carbonate (the crystal water contained in the rare earth carbonate can be accurately measured by an EDTA titration method) and gluconic acid according to the molar ratio of 1: 6. Adding small amount of water into the rare earth carbonate, and stirring to make the rare earth carbonate paste. Gluconic acid is dissolved in water to make a saturated solution (it is also possible to use dilute aqueous solutions of gluconic acid for the reaction, but more water must be evaporated to precipitate the product, which wastes fuel and prolongs the preparation reaction time). Adding the gluconic acid aqueous solution into the rare earth carbonate paste, and stirring the mixture at the temperature of 40-50 ℃ to react. During the reaction, bubbles of carbon dioxide are continuously generated to escape. When no bubble escaped, the preparation reaction was essentially complete. And then, continuing the reaction for 30-50 minutes to fully finish the reaction. Then, evaporating to concentrate the product, filtering, and exposing to airNatural drying or drying under infrared lamp to shorten drying time. The yield of the product rare earth gluconate complex reaches 92.6-94.3%. Has a chemical formula Ln (C)₆H₁₁O₇)₃。

The preparation method of the high-efficiency growth-promoting series gluconic acid rare earth complex fish bait additive has the following advantages: (1) the chemical reaction of the preparation is single, and no side reaction exists; (2) the purity of the target product is high, and an additional separation process is not needed; (3) the operation is simple, the mastering and the industrialization are easy to realize; (4) the required equipment is simple, the investment is low and the cost is low.

The application of the efficient series of growth-promoting gluconic acid rare earth complex bait additives disclosed by the invention can be expected to be beneficial to improving the situation that bait feeding falls behind in China and make a contribution to the development of fishery. Secondly, the rare earth resources in China are very abundant and can be first in the world. However, the rare earth application industry in China is quite laggard, especially the high-tech industry. This results in a large backlog of rare earth products in China, and the products are forced to be cheap and exported as primary products with low scientific and technological content, which causes great loss in China. The preparation and application of the rare earth gluconate complex fish bait additive provided by the invention opens up a new application field for rare earth, and has very important significance for reversing the passive situation of rare earth industry in China and changing the resource advantage into economic and technical advantages.

Detailed Description

The invention is further illustrated by the following examples.

Example 1

Lanthanum carbonate (the amount of crystal water contained can be accurately determined by EDTA titration) is accurately weighed as 1 mol, and gluconic acid is weighed as 6 mol. Adding a small amount of water to stir the lanthanum carbonate into paste, preparing the gluconic acid into a saturated aqueous solution, and adding the saturated aqueous solution into the lanthanum carbonate paste. The mixture is placed on a constant-temperature magnetic stirrer at 40 ℃ in a reactor and reacts while stirring. During the reaction, lanthanum carbonate is continuously dissolved, and carbon dioxide bubbles are released. When the carbon dioxide bubbles stopped escaping (at this time, the reactor became a transparent aqueous solution), the reaction was continued for another 30 minutes to complete the reaction sufficiently. Then, the mixture is evaporated and concentrated to separate out a solid target product. Filtering, and naturally drying in air to obtain lanthanum gluconate solid complex with chemical formula of La (C)₆H₁₁O₇)₃The yield thereof was found to be 95.6%.

Example 2

1 mol of lanthanum carbonate (the amount of crystal water contained can be accurately measured by EDTA titration) and 6 mol of gluconic acid are accurately weighed respectively. Adding a small amount of water to stir the lanthanum carbonate into paste, preparing the gluconic acid into saturated solution, and adding the saturated solution into the lanthanum carbonate paste. The mixture was placed in a reactor on a constant temperature magnetic stirrer at 50 ℃ and reacted while stirring. During the reaction, lanthanum carbonate is continuously dissolved, and carbon dioxide bubbles are released. When the carbon dioxide bubbles stopped escaping (at this time, the reactor became a transparent aqueous solution), the reaction was continued for another 50 minutes to complete the reaction sufficiently. Then evaporating and concentrating to separate out a solid target product. Filtering, and naturally drying in air to obtain lanthanum gluconate solid complex with chemical formula of La (C)₆H₁₁C₇)₃The yield thereof was found to be 93.4%.

Example 3

1 mol of lanthanum carbonate (the amount of crystal water contained can be accurately measured by EDTA titration) and 6 mol of gluconic acid are accurately weighed respectively. Adding a small amount of water to stir the lanthanum carbonate into paste, preparing the gluconic acid into saturated solution, and adding the saturated solution into the lanthanum carbonate paste. The mixture is placed on a constant-temperature magnetic stirrer at the temperature of 45 ℃ in a reactor and reacts while stirring. During the reaction, lanthanum carbonate is continuously dissolved, and carbon dioxide bubbles are released. When the carbon dioxide bubbles stopped escaping (at this time, the reactor became a transparent aqueous solution), the reaction was continued for another 50 minutes to complete the reaction sufficiently. Then evaporating and concentrating to separate out a solid target product. Filtering, drying under infrared lamp to obtain lanthanum gluconate solid complex with chemical formula of La (C)₆H₁₁C₇)₃The yield thereof was found to be 93.8%.

Example 4

1 mol of cerium carbonate (the amount of crystal water contained can be accurately measured by EDTA titration) and 6 mol of gluconic acid are accurately weighed respectively. Adding a small amount of water to stir the cerium carbonate into paste. The rest of the procedure was the same as in example 1. Obtaining the cerous gluconate solid complex to be synthesized, wherein the chemical formula is Ce (C)₆H₁₁C₇)₃The yield thereof was found to be 94.3%.

Example 5

1 mol of praseodymium carbonate (the amount of crystal water contained in the praseodymium carbonate can be accurately measured by an EDTA titration method) and 6 mol of gluconic acid are accurately weighed respectively. Adding a small amount of water to stir the praseodymium carbonate into paste. The rest of the procedure was the same as in example 1. Obtaining the praseodymium gluconate solid complex to be synthesized, wherein the chemical formula is Pr (C)₆H₁₁C₇)₃The yield thereof was found to be 94.1%.

Example 6

1 mol of neodymium carbonate (the amount of crystal water contained can be accurately measured by EDTA titration) and 6 mol of gluconic acid are accurately weighed respectively. Adding a small amount of water to stir the neodymium carbonate into paste. The rest of the procedure was the same as in example 1. Obtaining the neodymium gluconate solid complex to be synthesized, wherein the chemical formula of the neodymium gluconate solid complex is Nd (C)₆H₁₁C₇)₃The yield thereof was found to be 93.5%.

Example 7

1 mol of samarium carbonate (the amount of crystal water contained in the samarium carbonate can be accurately measured by EDTA titration) and 6 mol of gluconic acid are accurately weighed respectively. Adding a small amount of water to stir the samarium carbonate into paste. The rest of the procedure was the same as in example 1. Obtaining the samarium gluconate solid complex to be synthesized, wherein the chemical formula of the samarium gluconate solid complex is Sm (C)₆H₁₁C₇)₃The yield thereof was found to be 93.8%.

Claims

1. A rare earth gluconate complex bait additive has a chemical formula as follows:

Ln(C₆H₁₁O₇)₃

wherein Ln is La, Ce, Pr, Nd, Sm.

2. A process for preparing a bait additive as claimed in claim 1, which comprises the chemical reaction of:

the preparation process comprises the following steps: the mol ratio of the rare earth carbonate to the gluconic acid is 1: 6, and the rare earth carbonate is added with water and stirred into paste; mixing glucoseDissolving acid in water to prepare a solution, adding a gluconic acid aqueous solution into the rare earth carbonate paste, stirring at 40-50 ℃ until no bubbles escape, continuing to react for 30-50 minutes, evaporating, filtering, and naturally drying to obtain a product.

3. The method of claim 2, wherein the gluconic acid solution is a saturated aqueous solution.

4. The method of claim 2, wherein the drying is infra-red drying.