CN1823614A

CN1823614A - Phosphorus supple menting agent having controlled slow-release type phosphorus, its preparation and use method

Info

Publication number: CN1823614A
Application number: CNA2006100501138A
Authority: CN
Inventors: 夏枚生; 胡彩虹; 潘金敏
Original assignee: Zhejiang University ZJU
Current assignee: Zhejiang University ZJU
Priority date: 2006-03-31
Filing date: 2006-03-31
Publication date: 2006-08-30
Anticipated expiration: 2026-03-31
Also published as: CN100569092C

Abstract

A P-complementing forage additive containing the controlled slow releasing P is an active P contained bimetal oxide prepared from phosphate or hydrogen phosphate through calcining hydrotalcite to obtain bimetal oxide, adsorption, ionic exchange reaction, filtering, drying and pulverizing.

Description

The benefit phosphorus agent of controlled release type phosphorus and preparation method and purposes

Technical field

The present invention relates to a kind of agent of benefit phosphorus and preparation method and purposes of controlled release type phosphorus.

Background technology

Phosphorus is one of more mineral element of animal body intensive amount, and its requirement is only second to calcium, occupies critical role in growth of animal, growth.The phosphorus that wherein accounts for total phosphorus 85～88% is present in bone and the tooth, keeps the normal consistency of bone and tooth with calcium.And phosphorus is also as the component of energy-rich phosphate bond and phosphocreatine, participate in the energetic supersession of body, phosphorus participates in the absorption of lipid material, liposoluble vitamin and the formation of cell membrane in the mode of phosphatide, and, participate in the many important life process of body as the constituent of inhereditary material and some enzymes.Phosphorus shortage or deficiency can cause the slow or stagnation of growth of animal in the daily ration, and osteopathy takes place, and cause serious consequences such as death when serious.

Lack the phytase of hydrolysis phytic acid in nonruminant such as pig and bird and the fish alimentary canal, lower to the utilization rate of phosphorus in the plant feed, must be by adding the needs that livestock and poultry phosphorus is satisfied in the phosphorus source.Phosphorus source commonly used in the feed comprises bone meal and phosphoric acid salt.Bone meal is that the bone by animal processes, in feed, be used as calcium, the use of phosphorus fill-in, but because of composition changes greatly, the source is unstable, and foreign odor often arranged, the animal bone purchaser who more has is because of avoiding the fly maggot breeding, often sprays some medicaments and causes bone meal band poison, think on the feed industry that abroad the bone meal class is to cause the immediate cause of rabid ox disease, so its use amount reduces gradually.Phosphoric acid salt mainly comprises calcium dihydrogen phosphate, calcium monohydrogen phosphate, tricalcium phosphate etc.The biological value in phosphorus source not only influences the culturing economic benefit, and can not will be excreted with ight soil by the phosphorus that animal absorbs, and causes the pollution to environment of phosphor resource waste and phosphorus.

Bimetallic oxide is a kind of synthetic material who is made up of the metal oxide of two kinds of different valence state, is called for short LDO (Layered Double Oxides).It has the shepardite of being similar to (Mg (OH) ₂) layer structure, its predecessor is a hydrotalcite-based compound, also is called as anionic clay.The chemical structure of general formula of hydrotalcite is:

M ²⁺ _1-xM ³⁺ _x(OH) ₂] ^x+[A ^n- _x/n·mH ₂O]

M wherein ²⁺Be Mg ²⁺, Zn ²⁺, Fe ²⁺, Mn ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Ca ²⁺Deng divalent metal; M ³⁺Be Al ³⁺, Fe ³⁺, Cr ³⁺, Co ³⁺, Ti ³⁺Deng trivalent metal cation; A ^N-Be CO ₃ ^2-, Cl ^-, NO ₃ ^-, SO ₄ ^2-Deng anion; X=0.5～0.17; M ²⁺/ M ³⁺=1～5.Above structural formula can be regarded as divalent metal in the shepardite by the product that trivalent metal cation partly substitutes, and is the positive charge of balanced structure layer, between structure sheaf again filling anion, also have hydrone in addition.Existing more bibliographical information the preparation method of hydrotalcite, as coprecipitation or hydro-thermal method etc.

Hydrotalcite will destroy its layer structure 450 ℃～550 ℃ following calcinings, the bimetallic oxide that obtains mixing (LDO).Bimetallic oxide can come the restoration and reconstruction hydrotalcite structure by anion and the hydrone in the absorption environment, and because of having bigger specific area and pore volume, acceptant object.Bimetallic oxide after the roasting has bigger specific area than its predecessor, and has structure " memory " effect, promptly reuptakes anion and make it recover original layer structure in water environment.

Summary of the invention

The agent of benefit phosphorus and preparation method and the purposes that the purpose of this invention is to provide a kind of controlled release type phosphorus.

The benefit phosphorus agent of controlled release type phosphorus is a kind of bimetallic oxide that contains active phosphorus, and by weight percentage, the content of phosphorus in bimetallic oxide is 5～30%.

Preparation method's step of the benefit phosphorus agent of controlled release type phosphorus is as follows:

1) with hydrotalcite at 450～550 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to again greater than 400 orders, add water and stir, make concentration and be 1%～10% suspension slurry;

2) be the phosphate of bimetallic oxide weight 6～35% with phosphorus content, be pre-configured to the aqueous phosphatic of 0.1～1.0mol/L, slowly add in the suspension slurry of step 1) room temperature reaction 5～10 hours down in stirring;

3) the centrifugal or filtering means dehydration of suspension slurry step 2);

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

The hydrotalcite that uses in the invention can be the commercial goods, also can be according to prior art for preparing, and its technology of preparing is well-known.The hydrotalcite chemical structure of general formula is: [M ²⁺ _1-xM ³⁺ _x(OH) ₂] ^X+[A ^N- _X/nMH ₂O], wherein, bivalent metal ion M ²⁺Be Mg ²⁺, Zn ²⁺, Fe ²⁺, Mn ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Ca ²⁺In any, trivalent metal ion M ³⁺Be Al ³⁺, Fe ³⁺, Cr ³⁺, Co ³⁺, Ti ³⁺In any; A ^N-Be CO ₃ ^2-, Cl ^-, NO ₃ ^-, SO ₄ ^2-In any; X=0.5～0.17; M ²⁺/ M ³⁺=1～5.Bimetallic oxide is for to form hydrotalcite at 450～550 ℃ of temperature lower calcinations.

Among the preparation method of the present invention, said phosphate can be sodium phosphate, potassium phosphate, dibastic sodium phosphate or potassium hydrogen phosphate.

Preparation method's slurries dewatering process can be suited measures to local conditions, and selects for use centrifugal or method such as filtration is dewatered.The filter cake of dehydration back gained can use conventional drying plant drying.The benefit phosphorus agent of the controlled release type phosphorus after the oven dry is block, can select for use conventional disintegrating apparatus to be crushed to granularity greater than 300 orders.

The benefit phosphorus agent of controlled release type phosphorus is as the benefit phosphorus feed addictive of livestock and poultry, aquatic livestock, cattle and sheep.

Advantage of the present invention is:

(1) utilize bimetallic oxide to come the character of restoration and reconstruction hydrotalcite structure layer structure to come load phosphorus by the absorption phosphate radical anion, implementation method is easy, and production cost is lower.

(2) because bimetallic oxide has good biocompatibility and characteristics such as gastrointestinal tract mucous compatibility, interlayer interchangeability, high surface and bigger serface, make it that the phosphorus of institute's load is had the control slow releasing function, thereby improved the absorption rate of phosphorus greatly, reduced the pollution of phosphor resource waste and phosphorus environment.

(3) be that the benefit phosphorus agent of carrier is easy to mix with feed with the bimetallic oxide, form even disperse system, easy to use.

The specific embodiment

The present invention is further described in conjunction with following example.

Embodiment 1

1) with commercially available hydrotalcite at 450 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to 400 orders again, add water and stir, make concentration and be 10% suspension slurry;

2) be the sodium phosphate of bimetallic oxide weight 6% with phosphorus content, be pre-configured to the sodium phosphate aqueous solution of 0.1mol/L, slowly add in the suspension slurry of step 1) room temperature reaction 5 hours down in stirring;

3) suspension slurry centrifugal dehydration step 2);

4) filter cake of step 3) gained is dried, is crushed to 300 orders, obtain the benefit phosphorus agent of controlled release type phosphorus.The content of phosphorus in bimetallic oxide is 5%.

Embodiment 2

1) with commercially available hydrotalcite at 550 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to 500 orders again, add water and stir, make concentration and be 1% suspension slurry;

2) be the potassium phosphate of bimetallic oxide weight 35% with phosphorus content, be pre-configured to the potassium phosphate aqueous solution of 1.0mol/L, slowly add in the suspension slurry of step 1) room temperature reaction 10 hours down in stirring;

3) suspension slurry filtering means dehydration step 2);

4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the benefit phosphorus agent of controlled release type phosphorus.The content of phosphorus in bimetallic oxide is 30%.

Embodiment 3

Preparation: according to " magnalium type hydrotalcite hydro-thermal synthetic " (Xie Hui rectifys the celebrating pool, section snow. applied chemistry, 2001, method 18:70-72) prepares hydrotalcite.

1) with the hydrotalcite that obtains in the preliminary step at 500 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to 600 orders again, add water and stir, make concentration and be 5% suspension slurry;

2) be the dibastic sodium phosphate of bimetallic oxide weight 20% with phosphorus content, be pre-configured to the dibastic sodium phosphate aqueous solution of 0.5mol/L, slowly add in the suspension slurry of step 1) room temperature reaction 8 hours down in stirring;

3) suspension slurry centrifugal dehydration step 2);

4) filter cake of step 3) gained is dried, is crushed to greater than 300 orders, obtain the benefit phosphorus agent of controlled release type phosphorus.The content of phosphorus in bimetallic oxide is 17%.

Embodiment 4

Preparation: according to " binary metal houghite synthetic and as the Study on adsorption properties of presoma " (Guo Zhiqiang, Ni Zheming, Yu Weihua to NOx, Wang Ligeng, Ge Zhonghua. the Materials Science and Engineering journal, 2004,22 (6): method 878-880) prepares hydrotalcite.

1) with the hydrotalcite that obtains in the preliminary step at 480 ℃ of temperature lower calcinations, make bimetallic oxide, be ground to 500 orders again, add water and stir, make concentration and be 6% suspension slurry;

2) be the potassium hydrogen phosphate of bimetallic oxide weight 15% with phosphorus content, be pre-configured to the potassium hydrogen phosphate aqueous solution of 0.8mol/L, slowly add in the suspension slurry of step 1) room temperature reaction 6 hours down in stirring;

3) suspension slurry centrifugal dehydration step 2);

4) filter cake of step 3) gained is dried, is crushed to 300 orders, obtain the benefit phosphorus agent of controlled release type phosphorus.The content of phosphorus in bimetallic oxide is 13%.

The benefit phosphorus agent of controlled release type phosphorus is as the benefit phosphorus feed addictive of livestock and poultry, aquatic livestock, cattle and sheep.Using method: with pulverous controlled release type phosphorus, admix in livestock and poultry, aquatic livestock, the cattle and sheep feed (in phosphorus) by following additive capacity: pig 0.15～0.6%, egg fowl 0.30～0.40%, poultry 0.30～0.45%, aquatic livestock 0.3～0.9%, cattle and sheep 0.2～1.0%.

Claims

1. the benefit phosphorus agent of a controlled release type phosphorus is characterized in that it is a kind of bimetallic oxide that contains active phosphorus, and by weight percentage, the content of phosphorus in bimetallic oxide is 5～30%.

2. the benefit phosphorus agent of a kind of controlled release type phosphorus according to claim 1 is characterized in that said bimetallic oxide is for to form hydrotalcite at 450～550 ℃ of temperature lower calcinations.

3. the benefit phosphorus agent of a kind of controlled release type phosphorus according to claim 2 is characterized in that said hydrotalcite chemical structure of general formula is: [M ²⁺ _1-xM ³⁺ _x(OH) ₂] ^X+[A ^N- _X/nMH ₂O], wherein, bivalent metal ion M ²⁺Be Mg ²⁺, Zn ²⁺, Fe ²⁺, Mn ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Ca ²⁺In any, trivalent metal ion M ³⁺Be Al ³⁺, Fe ³⁺, Cr ³⁺, Co ³⁺, Ti ³⁺In any; A ^N-Be CO ₃ ^2-, Cl ^-, NO ₃ ^-, SO ₄ ^2-In any; X=0.5～0.17; M ²⁺/ M ³⁺=1～5.

4. the preparation method of the benefit phosphorus agent of a kind of according to claim 1 controlled release type phosphorus is characterized in that the step of method is as follows:

3) the centrifugal or filtering means dehydration of suspension slurry step 2);

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

5. the preparation method of the benefit phosphorus agent of a kind of controlled release type phosphorus according to claim 4 is characterized in that said hydrotalcite chemical structure of general formula is: [M ²⁺ _1-xM ³⁺ _x(OH) ₂] ^X+[A ^N- _X/nMH ₂O], wherein, bivalent metal ion M ²⁺Be Mg ²⁺, Zn ²⁺, Fe ²⁺, Mn ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Ca ²⁺In any, trivalent metal ion M ³⁺Be Al ³⁺, Fe ³⁺, Cr ³⁺, Co ³⁺, Ti ³⁺In any; A ^N-Be CO ₃ ^2-, Cl ^-, NO ₃ ^-, SO ₄ ^2-In any; X=0.5～0.17; M ²⁺/ M ³⁺=1～5.

6. the preparation method of the benefit phosphorus agent of a kind of controlled release type phosphorus according to claim 4 is characterized in that said phosphate is sodium phosphate, potassium phosphate, dibastic sodium phosphate or potassium hydrogen phosphate.

7. the purposes of the benefit phosphorus agent of a kind of controlled release type phosphorus as claimed in claim 1 is characterized in that the benefit phosphorus feed addictive as livestock and poultry, aquatic livestock, cattle and sheep.