CN1250103C

CN1250103C - Fish bait additive of complexes of rare earth and lactic acid, as well as preparation method

Info

Publication number: CN1250103C
Application number: CNB2004100111142A
Authority: CN
Inventors: 牛春吉; 王众; 牛盈赞
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2004-10-08
Filing date: 2004-10-08
Publication date: 2006-04-12
Anticipated expiration: 2024-10-08
Also published as: CN1600148A

Abstract

The present invention belongs to a fish bait additive of a rare earth and lactic acid complex and a preparation method. The additive is a complex of rare earth and lactic acid, with the chemical formula of LnL3, wherein Ln is La, Ce, Pr and Nd or mixed light rare earth, and L is a lactic acid radical. The present invention has the raw materials of rare earth oxide, mixed light rare earth chloride and lactic acid of the feed grade, chemical pure hydrochloric acid and chemical pure ammonia water. In the method, the rare earth oxide is made into a water solution thereof and added with the ammonia water till rare earth completely precipitates, and after filtration and water washing till no chlorine ion exists, rare earth hydroxide is obtained. The mixed light rare earth chloride is added with the ammonia water till rare earth completely precipitates, and after filtration and water washing till no chlorine ion exists, mixed light rare earth hydroxide is obtained. The rare earth hydroxide or the mixed light rare earth is added with water to be made into a suspension. The lactic acid is also added with water to be made into a water solution. The lactic acid water solution is dripped into the rare earth hydroxide suspension with continuous stir. The reaction temperature is controlled to be 60 to 70 DEG C, and the reaction time is 3.5 to 4.5 hours. Excess solvent water is evaporated at the temperature of 45 DEG C, and the recovery rate of the target product is 90.6% to 93.2%.

Description

Rare earth lactic acid complex fish bait additive and preparation method thereof

Technical Field

The invention belongs to bait additives, and particularly relates to a high-efficiency rare earth lactic acid complex bait additive.

The invention also relates to an optimized preparation method of the high-efficiency bait additive.

Background

The developed fish farming industry has great significance for improving the dietary structure of people in China and further improving the health level of people. Especially, under the condition that the natural fish resources are in short supply with the increase of the population, the significance of developing the fish farming industry is particularly important. The developed fish farming industry depends on the development of high-tech fish baits and additives. Rare earth resources in China are very rich, and various rare earth products far exceed the needs of domestic markets, so that a new application field of rare earth is urgently needed to be developed. The high-efficiency rare earth lactic acid complex fish bait additive opens up a new high-technology application field for rare earth, thereby being beneficial to changing the passive situation of the rare earth industry in China and changingthe resource advantage into the economic and technical advantage. The feed industry in China is also urgently to be developed, and some high-technology baits and additives are required to be quickly twisted depending on the situation of import, so that the research and development of high-efficiency feeds and additives with own intellectual property rights in China are imperative. The research and development of the high-efficiency rare earth lactic acid complex bait additive provided by the invention make a very successful effort for the research and development.

The important roles of baits and additives thereof are increasingly recognized, so the development of baits and additives is rapidly advanced. The development and application of the bait and the additive promote the rapid development of the breeding industry. The method is characterized in that the development of general baits and additives is more (such as Chinese patent application numbers 89107914 and 92110698), while the development of baits and additives for promoting growth with high efficiency is less; secondly, the development of fish essential nutrient baits and additives is more (such as Chinese patent application No. 87102566), while the development of trace element bait additives (such as Chinese patent application No. 95110754) is relatively less; finally, the development of fish baits and additives using rare earth growth promotion has been started (e.g., chinese patent application No. 02123909.6), but is still in the beginning, and particularly, carriers of rare earth elements as bait additives are yet to be further optimized. On the basis of earlier work, a carrier is further optimized, and the efficient rare earth lactic acid complex bait additive with the growth promoting effect is developed. The research and development of the high-efficiency rare earth lactic acid complex fish bait additive have important significance for promoting the feed and the additive to step into high technical level in China.

Disclosure of Invention

One of the purposes of the invention is to provide a novel efficient growth-promoting rare earth lactic acid complex bait additive.

The invention also aims to provide a preparation method of the high-efficiency growth-promoting rare earth lactic acid complex fish bait additive.

The invention relates to a high-efficiency rare earth lactic acid complex fish bait additive based on the following scientific principles. (1) The rare earth elements have the effects of promoting growth and increasing yield of plants and animals. The latest research results of rare earth biological inorganic chemistry and rare earth biological chemistry and the production practice of agriculture and animal husbandry in China already reveal that the rare earth elements have obvious growth promoting and yield increasing effects on plants and animals. The results of in vivo and in vitro experiments show that the rare earth elements can enhance the cell synthesis and secretion functions of growth hormone cells, thereby leading to the obvious increase of the content of the growth hormone. Animal growth hormone is directly related to growth and development of the animal growth hormone. The rare earth elements can also promote the growth of crops and increase the yield, such as vegetables, fruits and grain crops. It also has growth promoting effect on livestock and poultry, such as obvious increase of broiler weight, and high milk yield of milk cow. (2) The high efficiency of the bait additive and the principle that the carrier is not dense. The effectiveness of the microelement-based bait additive depends on the carrier of the microelements. The carrier of trace elements influences the absorption, distribution, excretion and performance of trace elements in the body of animals. The excellent carrier can make the trace elements be effectively absorbed and utilized by animals, and does not produce other side effects. The invention screens out lactic acid as a carrier of the rare earth element, thereby improving the absorption of the rare earth element and improving the availability of the fish body to the rare earth element. Based on the two principles, the rare earth lactic acid complex bait additive for efficiently promoting growth is prepared.

The high-efficiency rare earth lactic acid complex bait additive is a complex of rare earth and lactic acid, and has the chemical formula as follows:

LnL₃

where Ln is La, Ce, Pr, Nd or mixed light rare earth, and L is lactate. The raw materials used were as follows: rare earth oxide La₂O₃、CeO₂、Pr₆O₁₁Or Nd₂O₃The purity is 99%; mixing baotite with light rare earth chloride; lactic acid, feed grade; hydrochloric acid, chemically pure; ammonia water, chemically pure. The high-efficiency rare earth lactic acid complex fish bait additive has many characteristics. The fish bait additive has high fish availability, strong growth promoting effect on fish, fast fish body increment, high survival rate and no other adverse side effects on fish.

The high-efficiency bait additive can be prepared by the following method. According to the amount of the prepared rare earth lactic acid complex bait additive, the chemical composition LnL of the bait additive₃Accurately weighing rare earth oxide and lactic acid respectively. Mixing rare earth oxide La₂O₃、CeO₂、Pr₆O₁₁Or Nd₂O₃Adding hydrochloric acid at a ratio of 1: 1 to dissolve the hydrochloric acid, and evaporating off excessive hydrochloric acid to obtain an aqueous solution. Then addAdding ammonia water until the rare earth is completely precipitated, filtering, and washing with water until no chloride ion exists to obtain the rare earth hydroxide. And adding ammonia water into the mixed light rare earth chloride until the rare earth is completely precipitated, filtering, and washing with water until no chloride ion exists to obtain the mixed light rare earth hydroxide. The rare earth hydroxide Ln (OH) obtained above was reacted₃Adding water to Ln ═ La, Ce, Pr, Nd or mixed light rare earth to prepare suspension. Lactic acid is also added with water to make an aqueous solution. Is arranged to obtainThe aqueous solution of lactic acid is added dropwise to the suspension of rare earth hydroxide under continuous stirring on a heated stirrer. Lactic acid reacts with rare earth hydroxides as follows:

the reaction temperature is controlled at 60-70 ℃. With the progress of the reaction, the rare earth hydroxide is continuously converted into a complex with lactic acid with the formation of water. After the lactic acid aqueous solution is dripped, the reaction is continued until the target product is generated quantitatively, and the reaction time is selected to be 3.5-4.5 hours. After the reaction is completed, the excess solvent water is evaporated to completely precipitate the target product. The evaporation mode can adopt normal pressure evaporation at 45 ℃. And after the target product is completely separated out, filtering and drying to obtain the target product. The drying mode includes natural drying in air or infrared lamp baking. The chemical formula of the target product rare earth lactic acid complex fish bait additive is LnL₃Ln is La, Ce, Pr, Nd or mixed light rare earth, L is lactate, and the recovery rate of the target product is 90.6-93.2%.

The preparation process is simple, has no side reaction, and has high purity and yield of the target product. The preparation process does not need large-scale complicated instruments and equipment, is easy to industrialize, and has less investment and great benefit.

Detailed Description

Example 1

Accurately weighing 0.01mole of lanthanum oxide and 0.06mole of lactic acid respectively, adding 1: 1 hydrochloric acid into lanthanum oxide to dissolve lanthanum oxide, and evaporating excessive hydrochloric acid to obtain aqueous solution; then adding ammonia water to the solutionCompletely precipitating lanthanum, filtering, and washing with water until no chloride ion exists to obtain La hydroxide; the hydroxide La (OH) obtained above was used₃Adding water to prepare a suspension; lactic acid is also added with water to make an aqueous solution. Placing the obtained La hydroxide suspension on a heating stirrer, dropwise adding an aqueous solution of lactic acid into the hydroxide suspension under continuous stirring, wherein the lactic acid reacts with the La hydroxide, and the reaction temperature is controlled at 60 ℃; as the reaction proceeds, La hydrogenThe oxide is continuously converted into a complex with lactic acid with the formation of water. After the lactic acid aqueous solution is added dropwise, the reaction is continued until the target product is generated quantitatively, and the reaction time is selected to be 3.5 hours. After the reaction is completed, the excess solvent water is evaporated to completely precipitate the target product. The evaporation mode can adopt normal pressure evaporation at 45 ℃. And after the target product is completely separated out, filtering and drying to obtain the target product. The drying mode is natural drying in the air. The chemical formula of the target productlanthanum lactic acid complex fish bait additive is LaL₃L ═ lactate, target product recovery 91.4%.

Example 2

Accurately weighed as 0.02mole lanthanum oxide and 0.12mole lactic acid, respectively. The reaction temperature was controlled at 65 ℃ and the rest of the procedure was the same as in example 1. The target product prepared has the chemical formula of LaL₃The recovery of the target product was 92.1%.

Example 3

Accurately weighed as 0.03mole lanthanum oxide and 0.18mole lactic acid, respectively. The reaction temperature was controlled at 70 ℃ and the rest of the procedure was the same as in example 1. The target product prepared has the chemical formula of LaL₃The recovery of the target product was 91.6%.

Example 4

Accurately weighed as 0.04mole lanthanum oxide and 0.24mole lactic acid, respectively. The reaction time was controlled to 4.0 hours, and the rest of the procedure was the same as in example 1. The target product prepared has the chemical formula of LaL₃，The recovery of the target product was 92.8%.

Example 5

Accurately weighed as 0.05mole lanthanum oxide and 0.30mole lactic acid, respectively. The reaction time was controlled to 4.5 hours, and the rest of the procedure was the same as in example 1. The target product prepared has the chemical formula of LaL₃The recovery of the target product was 93.2%.

Example 6

Accurately weighed as 0.01mole lanthanum oxide and 0.06mole lactic acid, respectively. The drying of the target product was carried out by infrared lamp baking, and the rest was the same as in example 1. The target product prepared has the chemical formula of LaL₃The recovery of the target product was 92.3%.

Example 7

Accurately weighed as 0.04mole cerium oxide and 0.12mole lactic acid, respectively. The rest of the procedure was the same as in example 1. The target product prepared has the chemical formula of CeL₃The recovery of the target product was 92.5%.

Example 8

Accurately weighed as 0.01mole praseodymium oxide and 0.18mole lactic acid, respectively. The rest of the procedure was the same as in example 1. The prepared target product has the chemical formula of PrL₃The recovery of the target product was 90.9%.

Example 9

Accurately 0.05mole of neodymium oxide and 0.30mole of lactic acid, respectively, were weighed. The rest of the procedure was the same as in example 1. The prepared target product has a chemical formula of NdL₃The recovery of the target product was 93.1%.

Example 10

Accurately weigh 0.08mole of mixed rare earth chloride and 0.24mole of lactic acid, respectively. The rest of the procedure was the same as in example 1. The target product prepared has the chemical formula of LnL₃(Ln ═ mixed letdown), the recovery of the desired product was 90.6%.

Claims

1. The rare earth lactic acid complex bait additive is characterized in that the rare earth lactic acid complex is a complex of rare earth and lactic acid, and the chemical formula of the rare earth lactic acid complex bait additive is as follows:

LnL₃

in the formula, Ln is La, Ce, Pr, Nd or mixed light rare earth, L is lactate, and the used raw materials are as follows: rare earth oxide La₂O₃、CeO₂、Pr₆O₁₁Or Nd₂O₃The purity is 99%; mixing baotite with light rare earth chloride; lactic acid, feed grade; hydrochloric acid, chemically pure; ammonia water, chemically pure.

2. A process for preparing the rare-earth lactic acid complex as claimed in claim 1, as an additive for fish bait, characterized in that rare-earth oxide La is added₂O₃、CeO₂、Pr₆O₁₁Or Nd₂O₃Adding hydrochloric acid at a ratio of 1: 1 to dissolve the hydrochloric acid, and evaporating excessive hydrochloric acid to obtain an aqueous solution; then adding ammonia water until the rare earth is completely precipitated, filtering, and washing with water until no chloride ion exists to obtain rare earth hydroxide; adding ammonia water into the mixed light rare earth chloride until the rare earth is completely precipitated, filtering, and washing with water until no chloride ion exists to obtain mixed light rare earth hydroxide; reacting rare earth hydroxide Ln (OH)₃Adding water into Ln ═ La, Ce, Pr, Nd or mixed light rare earth to prepare suspension; adding water into lactic acid to obtain water solution; placing the obtained rare earth hydroxide suspension on a heating stirrer, and dropwise adding an aqueous lactic acid solution into the rare earth hydroxide suspension under continuous stirring; the reaction temperature is controlled at 60-70 ℃, and the reaction time is 3.5-4.5 hours; after the reaction is finished, evaporating excessive solvent water at 45 ℃, filtering after the target product is completely separated out, naturally drying in the air or baking and drying by an infrared lamp to obtain the target product, wherein the chemical formula of the target product rare earth lactic acid complex fish bait additive is LnL₃Ln ═La, Ce, Pr, Nd or mixed light rare earth, L ═ lactate, the recovery rate of the target product is 90.6-93.2%.