CN102626181A - Calcium citrate organic feed additive and preparation method thereof - Google Patents

Abstract

The invention discloses a calcium citrate organic feed additive and a preparation method thereof. Calcium citrate is calcium citrate comprising four crystallization water as a main ingredient. The preparation method of the calcium citrate comprising the four crystallization water comprises the following steps of: (1), putting water in a reaction kettle to be boiled; (2), uniformly feeding citric acid into the reaction kettle, stirring for 3-10 min till completely dissolving, and keeping at 60-90 DEG C; (3), slowly and uniformly feeding light calcium carbonate, and stirring till completely reacting to obtain the calcium citrate ((C6H5O7)2Ca3)4H2O) comprising the four crystallization water; (4), precipitating; (5), dehydrating; (6), drying; (7), screening; and (8), checking and packaging. The calcium citrate ((C6H5O7)2Ca3)4H2O) comprising the four crystallization water is slightly soluble in water and has good dissolving property and high animal absorbance under the slight acid condition.

Description

Calcium citrate organic feed additive and preparation method thereof

Technical field

The present invention relates to a kind of production method of animal organic feed additive, particularly a kind of calcium citrate organic feed additive and preparation method thereof.

Background technology

China's feed industry begins flourish from the beginning of the eighties, the history of existing two more than ten years has reached 1.78 hundred million tons to China's feed total output in 2011 so far, occupies first in the whole world.The annual production of mixed feed reaches 5119.5 ten thousand tons.But compared with developed countries, also there are some problems in China's additive industry in fast development, and wherein the research and development of new varieties, novel form feed addictive lag behind the market demand far away.With regard to trace mineral supplement; In the production process of two more than ten years, adding inorganic microelements in a large number always; Because the reasons in structure of these inorganic microelements own causes that its biological value is lower, animal absorbs limited in one's abilityly, therefore needs very big addition, and animal real absorbent only be seldom one one; General uptake is merely below 1/3 of addition; The trace element that does not have to absorb excretes or is deposited on from the ight soil of animal in bone, liver even the muscle of animal, thereby has caused problems such as a large amount of wastings of resources, environmental pollution and food security, the health of harm humans.

Along with the development of feed industry and the progress of aquaculture, the organic trace element feed addictive has become the indispensable raw material of mixed feed.People are according to the different animals nutritional need; The feed addictives such as trace element that in mixed feed, add various dose come the balanced nutrients composition, promote animal to produce, improve product quality to reach, and improve food conversion ratio; Reduce feeding cost, the purpose of increasing economic efficiency.

Calcium is first mineral element in the animal body, and calcium accounts for the 1%-2% of the weight of animals.99% of calcium exists in bone and the tooth, and remaining calcium is present in the soft tissue body fluid.Obviously, calcium the growth of bone and tooth with maintain in play an important role, in addition, calcium also has many important biological functions.Calcium all has decisive role to the transmission of blood clotting, nerve impulse, the contraction of muscle, the activity of enzyme and the secretion of hormone etc.Rickets can take place when lacking calcium in young animal, and osteomalacia appears in adults when lacking calcium, and calcium, phosphorus ratio imbalance also can cause acalcicosis, and calcium deficiency also causes that breeding performonce fo animals descends simultaneously except that causing bone disorders.

On herding is produced, be main calcium source with inorganic calcium classes such as pulverized limestone, calcium carbonate and calcium monohydrogen phosphates mainly at present, wherein calcium carbonate is because calcium content is high, safety, effective, and particularly inexpensive advantage is used the most extensive.Although the calcium carbonate calcium content is high, and is cheap, because dissolution of calcium carbonate property is extremely low, its dissolving needs lower pH, must be under one's belt with a large amount of acid reaction generation ionized calcium after just can be absorbed.Calcium carbonate has acidophilia, in hydrochloric acid in gastric juice after, produce carbon dioxide and cause animal intestines and stomach flatulence.The calcium carbonate major part has drained with the difficulty soluble salt form, or deposition in animal body, causes the waste of raw material, and the calcium absorption is bad to be caused the calcium phosphorus ration imbalance and cause aphosphorosis.Especially young animal, digestive system development imperfection, stomach are secreted sour ability not as good as adults, and stomach inner pH value is higher than the pig that grows up, and directly influences its absorption to calcium.Especially early-weaned piglets, ablactation stress causes that stomach inner pH value significantly rises, and is unfavorable for growth.And inorganic calcium causes electrolytical imbalance easily, causes piglet white scour; Calcium carbonate also disturbs the absorption of inorganic ions such as iron, zinc simultaneously.

(molecular formula is C to calcium citrate ₁₂H ₁₀Ca ₃O ₁₄) as a kind of novel calcium preparation, be widely used in the medicine and the mankind at home and abroad and replenished the calcium.The U.S. is " in clinician's handbook on the desk 1993 version (PCR); Recommend to use calcium citrate as clinical calcium tonic commonly used, " U.S. food additive standard " version (PCC) and Japan's " japanese food additive official compendium " in 1996 sixth version in 1992 has also recorded this kind.In China's " Chinese food industrial standard compilation "; Food additives have recorded this product; Ministry of Health of China approval calcium citrate was a health food in 1997; Calcium citrate was approved for national new drug in China in 1998,1999 " Chinese family OTC guide " (in the effect and the purposes of calcium citrate have been done clear and definite explanation.Also there are clearly regulation in world's food in 1985 and agricultural organization/World Health Organization (FAO/WHO) to the security of calcium citrate, and acceptable daily intake (ADI) is not done particular provisions, does not in fact show toxicity.

With respect to calcium carbonate, the dissolubility of calcium citrate is good, is that 10 times of calcium carbonate (generally believe at present; The calcium source biological value that solubility is big more is high more), so strong unlike calcium carbonate to the hydrochloric acid in gastric juice dependence, even in water, can dissolve; Little to gastrointestinal irritation property, wholesomeness is high.It not only can be used as the calcium supplementing preparation of animal, simultaneously can also be as acidulant necessary in the animal body.Therefore, compare with inorganic calcium (like calcium carbonate and calcium monohydrogen phosphate), calcium citrate can significantly improve the biological value of calcium, can directly be absorbed by animal, and not influence the particularly absorption of iron of other mineral matter; Produce carbon dioxide with hydrochloric acid in gastric juice in not understanding, therefore can not cause flatulence and cause the discomfort of animal body.Simultaneously, citric acid is a kind of trophism acidulant, is the intermediate product of human body energy metabolism; Important biological function is arranged: being the important medium in the acetyl-CoA synthctic fat process, is one of important substance that constitutes in the mitochondria respiratory chain, can regulate the cAMP activity; Participate in a series of important reactions such as human body energy, structure and enzyme guarantee; Can reduce daily ration and animal alimentary canal pH value, change microbial bacteria group structure in the alimentary canal, it is active to improve digestive enzyme; Promote the absorption of vitamin, mineral element, improve the digestibility of nutriment.The experimental study that Yang Jun etc. (1999) absorb in the rat body with citric acid one malic acid calcium salt; The result shows; Calcium citrate various dose group feed calcium absorptivity with retain rate all apparently higher than calcium carbonate group with a kind of dosage, show that the absorption of calcium citrate in the rat body rate that retains obviously is superior to calcium carbonate.This explanation calcium citrate is a kind of desirable calcium preparation, has higher biologically active, and supplement calcium under the situation of other allowance of nutrients abundance, as the feed calcium source, can guarantee and promote the healthy growth and development of toy with calcium citrate effectively.

Calcium citrate has been widely used in the mankind and has replenished the calcium; Citric acid also has been widely used in the Production of Livestock and Poultry application as acidulant; Therefore, substituting traditional calcium carbonate with calcium citrate, is fully feasible as the calcium source in the livestock and poultry diet; For animal particularly stomach secrete the young animal of sour scarce capacity, calcium citrate will be a kind of calcium source of more high-quality.

Though but people know that calcium citrate is a kind of good calcium tonic, and does not know that calcium citrate also has difference along with the difference of molecular structure, because calcium citrate has several kinds of crystalline solid, 1, ((C ₆H ₅O ₇) 2Ca ₃) 4H ₂O (four crystallizations water); 2, ((C ₆H ₅O ₇) 2Ca ₃) 3H ₂O (three crystallizations water); 3, ((C ₆H ₅O ₇) 2Ca ₃) 2H ₂O (two crystallizations water); 4, ((C ₆H ₅O ₇) 2Ca ₃) H ₂O (crystallization water); 5, ((C ₆H ₅O ₇) 2Ca ₃) (anhydrous); In the calcium citrate of these several kinds of crystalline solid, what absorbed by animal the most easily is the calcium citrate of four crystallizations water, and different reactants and reaction condition obtain the citric acid of the different crystallizations water; So the calcium citrate of producing four crystallizations water has become the direction of people's research; In recent years, open source literature has also been reported the production method of some calcium citrates, for example:

1, [autograph] utilizes eggshell to produce Primary Study [author] Bin Dongmei of calcium citrate, is prone to really Ma Meihu; Luo Renzhi; [mechanism] [1] Hunan environmental organism Vocationl Technical College, [2] Agricultural University Of Hunan, [periodical name] modern food science and technology .2006; 22 (3) .-6-9,5 [digests] are for making full use of the CaCO in the eggshell ₃, adopt neutralisation to prepare calcium citrate, make inorganic calcium wherein be converted into organic calcium, carried out the influence experimental study of factors such as calcination condition, proportioning raw materials, reactant concentration, temperature, time to product yield and purity.The result shows: the optimum process conditions are respectively: eggshell is at 900 ℃ of calcining and decomposing 1-2h, and the CaO yield is more than 95%.The neutralization reaction condition: lime milk concentration 5%, citric acid concentration 50%, 60 ℃ of reaction temperatures, reaction time 1h, product yield is high, good, the safety non-toxic of quality.

2, [autograph] prepares research [author] Lin Liliwen strong Pan Rong pattern stone ripple [mechanism] Zhanjiang Normal University's chemical science dawn and the technical college of calcium citrate with shell; [periodical name] journal .2010 of Zhanjiang Normal University; 31 (6) .-95-98 [digest] are raw material with the shell, adopt a calcination method to prepare calcium citrate, and utilize orthogonal experiment that preparation condition is studied. the result shows: in the 10mL mass concentration is in the 0.20g.mL-1 citric acid; Add the oyster shell whiting after 1.0g calcines; Neutralization reaction under 60 ℃ of conditions, the productive rate of products obtained therefrom are 94.04%, and purity is 99.29%; Product meets the quality requirement of China's calcium additive basically through infrared and quality testing.

3, Chinese patent, application number: 92104844.0 applyings date: 1992.06.25 title: produce the method for high purity medical calcium citrate with ordinary student lime and edible citric acid, open (bulletin) number: CN1066443; Application (patent right) people: Hengda Trading Company, Chuansha, Shanghai; Address: No. 242, ring West Road, river, city proper and areas just outside its gates town, sea market Chuansha, invention (design) people: Yuan Jingcheng, summary; A kind of method of utilizing ordinary student lime and edible citric acid to produce the high purity medical calcium citrate; Technical characterictic is: with ordinary student lime and ammonium chloride and water wiring solution-forming by a certain percentage, through filter, the clarification back feeds carbon dioxide and carries out carbonization, then through dehydration, washing, dehydration, drying, cool off, pulverize, screen powder A; Again will be through the powder A after the above-mentioned processing and edible citric acid and water wiring solution-forming by a certain percentage; React at a certain temperature, after question response finishes fully, promptly get the high purity medical calcium citrate through dehydration, washing, dehydration, drying, screening.The high purity medical calcium citrate has high medical value as a kind of good calcium tonic.

4, Chinese patent; Application number: 201110233649.4 applyings date: 2011.08.16 title: the high preparation method that dissolves the crystal formation calcium citrate; Open (bulletin) number: CN102351688A open (bulletin) day: 2012.02.15 apply for (patent right) people: the Shandong perseverance is led to the bio tech ltd address: (design) people: Wang Yuanda is invented in industry park, Qinghe, Qinghe town, Accessories during Binzhou Huimin County, Shandong Province; Summary, a kind of preparation method of high molten crystal formation calcium citrate.Technical scheme: form: (one) raw material and proportioning: citric acid, calcium carbonate and 3.84: 3: 1 ratio mixings of water by following steps; (2) behind the mixing, put into temperature and be 20-50 ℃ agitated reactor, start chemical reaction 50-60 minute; (3) shut down 25-35 minute, chemical reaction is ripe; (4) start is 25-35 minute, and the height of emitting under the crystallization temperature dissolves the crystal formation calcium citrate; (5) filter, dry the back packed products.Beneficial effect: synthetic height dissolves crystal formation calcium citrate, molecular formula: Ca ₃H ₃(C ₆H ₅O ₇) ₂(HCO ₃) ₃, solubility 98% is soluble calcium, replenishes the calcium and controls the osteoporosis osteomalacia, humans and animals is prone to absorb, and available calcium citrate injection and calcium citrate oral liquid, uses and does not receive the restriction of indissoluble calcium citrate.

The preparation method of the calcium citrate that above-mentioned open source literature proposed can not obtain that dissolubility is not only good, trap but also four high water citric acid calcium, generally just obtains ((C ₆H ₅O ₇) 2Ca ₃) H ₂O, ((C ₆H ₅O ₇) 2Ca ₃) 2H ₂O, ((C ₆H ₅O ₇) 2Ca ₃) 3H ₂O, ((C ₆H ₅O ₇) 2Ca ₃) 4H ₂The mixture of O, for example document 1-3 utilizes eggshell or shell to produce calcium citrate, and neutralization reaction is all added lime (calcium oxide), and what obtain contains ((C ₆H ₅O ₇) 2Ca ₃) H ₂O, ((C ₆H ₅O ₇) 2Ca ₃) 2H ₂O is more, and these calcium citrates are water-soluble better, but dissolving under one's belt and absorption and bad; Document 4 is with citric acid, calcium carbonate and 3.84: 3: 1 ratio mixings of water, and 20-50 ℃ was reacted 50-60 minute; Obtain the high crystal formation calcium citrate that dissolves after the chemical reaction maturation; (be actually and contain ((C ₆H ₅O ₇) 2Ca ₃) H ₂O, ((C ₆H ₅O ₇) 2Ca ₃) 2H ₂The calcium citrate that O is more), at present bibliographical information is mostly thought ((C ₆H ₅O ₇) 2Ca ₃) 4H ₂O absorbs bad (document 4 also is such argumentation) to animal, and this is incomplete, should, because except the calcium citrate of four crystallizations water, the interior absorption of the calcium citrate animal stomach of other crystallization water is bad, and (as injection possibly be (C ₆H ₅O ₇) 2Ca ₃) H ₂O, ((C ₆H ₅O ₇) 2Ca ₃) 2H ₂O is better.Concrete reason can provide at following beneficial effect of the present invention.

So along with the continuous progress of society, the human living standard improves constantly; People's environmental consciousness and legal consciousness constantly strengthen, and the country and the public also continue to increase the management intensity and the degree of concern of animal feeding safety, therefore; Explore a kind of animal calcium-supplementing preparation of safe, efficient, environmental protection,, improve agroecological environment for improving China's animal husbandry integrated production capacity; Control and assurance food security from the source; Improve the survival and development of Feed Manufacturing industry, accelerate China's animal husbandry development, active operation significance is arranged.

Summary of the invention

The objective of the invention is the above deficiency that exists of pin and a kind of animal calcium-supplementing preparation safe, efficient, environmental protection is provided is calcium citrate organic feed additive and preparation method thereof, particularly organic feed additive of four crystallization water calcium citrates and preparation method thereof.

The present invention is achieved in that

The preparation method of the calcium citrate of four crystallizations water of the present invention is following:

Raw material and parts by weight below adopting: water: 60～80; Citric acid: 16～20; Precipitated calcium carbonate 10～15; Production stage:

(1) place in the agitated reactor water boiled;

(2) get citric acid and evenly drop into agitated reactor, stir 3-10 minute, keep 60-90 ℃ to dissolving fully; ,

(3) get precipitated calcium carbonate, slowly evenly drop into, stir,, obtain the calcium citrate ((C of four crystallizations water to complete reaction ₆H ₅O ₇) 2Ca ₃);

(4) deposition: put into the cooling of stainless steel pond, deposition;

(5) dehydration: the product that will cool off deposition is put into centrifuge dewatering;

(6) drying: the product introducing pneumatic drier that will take off water carries out drying, and baking temperature is controlled at 120 ℃～145 ℃;

(7) screening: dry cooling back screening;

(8) after the assay was approved, the packing of product, warehouse-in.

Chemical equation is:

C ₆H ₈O ₇+CaCO ₃→(C ₆H ₅O ₇) ₂Ca ₃·4H ₂O+CO ₂

Feed stripped consumption pig, ox, sheep is: perfect compound feed addition 3-5 kilogram per ton;

At poultry feed consumptions such as chicken and duck goose or rabbits be: perfect compound feed addition 2-3 kilogram per ton;

Above-described citric acid is the citric acid that does not contain heavy metal or harmful substance;

Above-described precipitated calcium carbonate (Light Calcium Carbonate) claim winnofil (Precipitated Calcium Carbonate again; Be called for short PCC); Not that common direct pulverizing of calcium carbonate stone obtains, but raw material sections such as lime stone are burnt generation lime and carbon dioxide, add water digestion lime generation milk of lime (main component is a calcium hydroxide) again; And then feed carbon dioxide carbonization milk of lime and generate precipitation of calcium carbonate, after dehydration, dry and pulverize and make; Perhaps carry out metathesis reaction with sodium carbonate and calcium chloride earlier and generate precipitation of calcium carbonate, make through dehydration, drying and pulverizing then.The particle control of precipitated calcium carbonate was 80 mesh sieves, also can adopt micropowder light calcium carbonate (1～5 μ m) or fine and lightweight calcium carbonate (0.1～1 μ m).

The calcium citrate ((C of four crystallizations water that above-mentioned chemical equation obtains ₆H ₅O ₇) 2Ca ₃) 4H ₂O, primary first-order equation contains four crystallization water content more than 95%, the calcium citrate of a spot of water, two water and three water, pH 5.5-7.5 is slightly soluble in water.

The method of inspection:

1, principle: pH greater than 12 medium in, a calcon carboxylic acid sodium salt indicator directing terminal is with disodium ethylene diamine tetraacetate standard solution titration calcium ion Ca ²⁺, excessive disodium ethylene diamine tetraacetate is captured the Ca with the indicator complexing ²⁺, the indicator that dissociates is judged the terminal point that reacts according to change color.

2, analytical procedure:

Take by weighing about 0.2 gram of sample, be accurate to 0.0002 gram, place 250 conical flasks, add 10ml water; The 2ml hydrochloric acid solution, to the sample dissolving, thin up adds triethanolamine solution 5ml to 100ml; Sodium hydroxide solution 15ml shakes up, and regulates pH greater than 13, adds calcon-carboxylic acid 0.1g; With the titration of disodium ethylene diamine tetraacetate standard titration solution, becoming pure blue to solution by aubergine is terminal point, carries out blank test simultaneously.

Disodium ethylene diamine tetraacetate standard titration solution: 0.05mol/l

Sodium hydroxide solution 1mol/l

Hydrochloric acid solution: 1+1

Triethanolamine solution: 30%

Calcon-carboxylic acid: take by weighing 10g in advance at 105-110 ℃ of sodium chloride of drying down, place mortar, add the 0.1g calcon-carboxylic acid, porphyrize mixes.

3. the result calculates

Calcium citrate content is represented with mass fraction % in the sample, calculates by formula (1):

$X_1=\frac{(V_1-V_2)\×F\×8.307}{m_1\×1000\×(100-X_4)}\×100---\left(1\right)$

V ₁-titration sample consumes the volume of disodium ethylene diamine tetraacetate standard titration solution, and unit is a milliliter (mL);

V ₂-titration blank solution consumes the volume of disodium ethylene diamine tetraacetate standard titration solution, and unit is a milliliter (mL);

F-disodium ethylene diamine tetraacetate standard titration solution actual concentrations and 0.05 ratio;

8.037-the edetate of every consumption 1mL0.05mol/L is equivalent to the Ca (C of 8.037mg ₆H ₅O ₇) ₂

m ₁The quality of-sample, unit is gram (g);

X ₄The loss on drying of-sample, %.

The mensuration of citric acid content in the above-mentioned calcium citrate

1, principle, in acid solution, potassium permanganate can be quantitatively with the citric acid oxidation, after reaction is accomplished, adds KI, makes remaining KI reaction generate free-iodine, with sodium thiosulfate standard solution titration free-iodine, calculates the content of citric acid with this.

Citric acid, anhydrous,

Hydrochloric acid solution: 1+1

Potassium permanganate: 0.1mol/l

Sodium thiosulfate standard solution 0.1mol/l

Sulfuric acid solution 20%

2, analytical procedure:

Take by weighing calcium citrate sample 1g, be accurate to 0.0002g, in the 100mL beaker, add 10mL water and dripping hydrochloric acid solution to sample dissolves, move in the 100mL volumetric flask, add water to scale, shake up; Pipette test solution 1.00mL with pipette, place the 250mL conical flask, add water 150mL, add sulfuric acid solution 10mL and manganese sulfate 1g; In water-bath, be heated to 70 ℃,, slowly add potassium permanganate standard liquid 25.0mL, in 70 ℃ of water-baths, place 10min constantly shaking down; With the flowing water cooling, add KI 2g, shake up, extremely faint yellow with the sodium thiosulfate standard solution titration; Add starch solution 2mL, continue titration and disappear for terminal point, calculate citric acid content through (2) formula to blue.

$X_3=\frac{(25-K\×V_5)\×T\×100}{m_3\×(100-X_4)}\×100---\left(2\right)$

The volume of 25-potassium permanganate standard liquid, unit are milliliter (mL);

The liquor potassic permanganate volume ratio that the K-1mL sodium thiosulfate standard solution is suitable;

V ₅-burette test solution consumes sulfuric acid sodium standard solution volume ratio, and unit is a milliliter (mL);

The anhydrous citric acid content that T-1mL potassium permanganate standard liquid is suitable, unit is every milliliter (g/mL) of gram;

m ₃The quality of-sample, unit is gram (g);

X ₄The loss on drying of-sample, %.

The mensuration of above-mentioned calcium citrate and citric acid content is being write the State Standard of the People's Republic of China, is write by the inventor.

The invention has the beneficial effects as follows:

The present invention is a kind of animal calcium citrate organic feed additive of safe, efficient, environmental protection.The calcium citrate ((C of four crystallizations water ₆H ₅O ₇) 2Ca ₃) be slightly soluble in water, but solubility property is good under slightly acidic condition, and the animal trap is high.

Why the calcium citrate ((C of four crystallizations water ₆H ₅O ₇) 2Ca ₃) 4H ₂O is slightly soluble in water; But solubility property is good under slightly acidic condition; Is the animal trap high? Mainly be that the calcium citrate that contains 1-3 the crystallization water is easy to water-soluble; When water-soluble the time, just become ionic condition, and the calcium of ionic condition absorbs not as the organic calcium good absorbing, the calcium citrate ((C of four crystallizations water of the present invention ₆H ₅O ₇) 2Ca ₃) 4H ₂O is ionic condition, but organic complex, get in the animal stomach after, generate absorbable organic calcium with the hydrochloric acid in gastric juice slow reaction, rather than ionized calcium, so the food and medicine standard of the U.S. is with ((C ₆H ₅O ₇) 2Ca ₃) 4H ₂O does not adopt the calcium citrate of 1-3 the crystallization water as calcium tonic, possibly be exactly this reason.

The inventor thinks that the calcium citrate of high-dissolvability of background technology document introduction can not make animal that trap is preferably arranged, and is exactly above-mentioned reason.

In addition, the present invention mainly is to control reaction temperature and keeps 60-90 ℃, reaction time 0.5-3 hour and baking temperature to be controlled at 120 ℃～145 ℃, just can guarantee to obtain ((C ₆H ₅O ₇) 2Ca ₃) 4H ₂O is more than 95%.

Description of drawings

Fig. 1 is calcium citrate organic feed additive flow process figure of the present invention.

As shown in the figure, calcium citrate production method of the present invention is to place in the agitated reactor water boiled; Get citric acid again and evenly drop into agitated reactor, stir 3-10 minute, keep 60-90 ℃ to dissolving fully; Get precipitated calcium carbonate then, slowly evenly drop into, stir,, obtain the calcium citrate ((C of four crystallizations water to complete reaction ₆H ₅O ₇) 2Ca ₃) 4H ₂O; Through deposition, dehydration, drying; , the screening, the check, the packing, obtain product.

The specific embodiment

Embodiment 1:

It is boiled in agitated reactor, to drop into 60 parts in water, gets citric acid and evenly drops into agitated reactor for 16 parts, stirs 3-10 minute to dissolving fully; Get 10 parts of the precipitated calcium carbonates of 80 mesh sieves then, slowly evenly dropped into, stirred, kept 60-90 ℃, reaction time 0.5-3 hour; Put into the cooling of stainless steel pond, deposition then.The product that cools off deposition is put into centrifuge dewatering; The product introducing pneumatic drier that will take off water again carries out drying, and baking temperature is controlled at 120 ℃～145 ℃, and dry cooling back screening after the assay was approved, is packaged to be product ((C ₆H ₅O ₇) 2Ca ₃) 4H ₂O, content are 96%.

Embodiment 2:

It is boiled in agitated reactor, to drop into 70 parts in water, gets citric acid and evenly drops into agitated reactor for 18 parts, stirs 3-10 minute to dissolving fully; Get 12 parts of the precipitated calcium carbonates of 80 mesh sieves then, slowly evenly dropped into, stirred, kept 60-90 ℃, reaction time 0.5-3 hour; Put into the cooling of stainless steel pond, deposition then.The product that cools off deposition is put into centrifuge dewatering; The product introducing pneumatic drier that will take off water again carries out drying, and baking temperature is controlled at 120 ℃～145 ℃, and dry cooling back screening after the assay was approved, is packaged to be product (C ₆H ₅O ₇) 2Ca ₃) 4H ₂O, content are 97%.

Embodiment 3:

It is boiled in agitated reactor, to drop into 80 parts in water, gets citric acid and evenly drops into agitated reactor for 20 parts, stirs 3-10 minute to dissolving fully; Get 15 parts of the precipitated calcium carbonates of 80 mesh sieves then, slowly evenly dropped into, stirred, kept 60-90 ℃, reaction time 0.5-3 hour; Put into the cooling of stainless steel pond, deposition then.The product that cools off deposition is put into centrifuge dewatering; The product introducing pneumatic drier that will take off water again carries out drying, and baking temperature is controlled at 120 ℃～145 ℃, and dry cooling back screening after the assay was approved, is packaged to be product (C ₆H ₅O ₇) 2Ca ₃) 4H ₂O, content are 96%.

Product quality indicator:

Project	Index
		Calcium citrate (in Ca3 (C6H5O7) 2) content, %	≥97.0
Calcium (in Ca) content, %	≥23.40
		Loss on drying, %	≤13.0
Total arsenic (in As), mg/kg	≤5.0
		Plumbous (in Pb), mg/kg	≤10.0
Mercury (in Hg), mg/kg	≤0.5
		Cadmium (in Cd), mg/kg	≤2.0
Chromium (in Cr), mg/kg	≤10.0

Practical function

One, the calcium citrate feeding experiment of four crystallizations water

Nanjing Zeweier Feed Co., Ltd. entrusts Animal nutrition research institute of Sichuan Agricultural University to carry out zoopery, and the biological value of feed addictive calcium citrate is evaluated with regard to the influence of feed addictive calcium citrate to breeding performonce fo animals.Result of the test is following: (for ease, employed calcium citrate is that the calcium citrate of four crystallizations water all abbreviates calcium citrate as)

(1) experiment material: the calcium citrate of experimental group is Nanjing Zeweier Feed Co., Ltd.'s self-control; Positive control group precipitated calcium carbonate is commercially available feed grade additive.

(2) experimental animal and grouping:

Select 90 (body weight: 7.0 ± 0.5kg) of 21 age in days weanling pigs.Wherein 84 are divided into 14 processing at random, and each handles 3 repetitions, and each repeats 2 pigs.Remain 6 pigs, be assigned randomly to calcium level and be NRC standard (Ca 0.8%) 2 processed group respectively repeat each 1.

(3) experimental design:

(4) test daily ration: basal diet is formed and trophic level

Raw material	Basal diet (%)
		Corn	29.39
Popcorn	22.39
		Expanded soybean	10.00
Dregs of beans	10.00
		FSPC	5.00
Fish meal	5.00
		Whey powder	10.00
Sucrose	1.50
		Glucose	1.50
Bentonite	3.33

Sodium dihydrogen phosphate	0.33
		Salt	0.35
The DL-methionine	0.07
		FE-5	0.34
Threonine	0.11
		Tryptophan	0.04
Choline	0.10
		Add in the ore deposit	0.50
Multidimensional	0.05
		Sulfuric acid Bacillus adhaerens (10%)	0.002
Add up to	100
		Trophic level (%)
Crude protein CP	19.83
		Digestible energy DE (MJ/kg)	14.09
Calcium Ca	0.37
		Total phosphorus	0.60
Available phosphorus	0.40
		Total lysine Lys	1.34
But digestible lysine D-Lys	1.19
		Total sulfur-containing amino acid DSAA	0.68
Threonine	0.74
		Tryptophan	0.22

(5) feeding and management

Test is carried out at Animal nutrition research institute of Sichuan Agricultural University test site piglet child care house.The child care house adopts slatted floor child care equipment, and the house temperature control is at 22～25 ℃, and relative humidity is controlled at 65%～70%.Test is cleaned completely, is washed away and sterilize pig house and the various utensil of feeding the last week, sprays facilities such as ground, fence, pig groove with caustic soda.Peracetic acid is used in daily pig house sterilization.Duration of test keeps colony house ventilation, cleaning, drying.Raised in advance 3 days, and just trying phase 35d.Examination pig day is fed 4 times (8:00,12:00,16:00,20:00), and the amount of feeding shows a small surplus with hopper after eating and exceeds, and freely drinks water.

(6) testing index and method

1. the piglet production performance 4. 6. 7.

Feed intake, daily gain, feedstuff-meat ratio:

Just try phase 28d and weighing, writing down the feed addition every day.Calculate average daily ingestion amount, average daily gain, average daily ingestion amount/average daily gain calculating feedstuff-meat ratio.

The diarrhoea index: the diarrhoea head multiply by corresponding diarrhoea score and calculates.

2. blood sample:

Off-test, after early 8:00 weighed to the examination pig on an empty stomach, all pigs were only taken a blood sample, separation of serum.Measure Ca, P, alkaline phosphatase activities in the serum.

3. butcher index: test 8d 8:00 early, in Ca 0.8% horizontal group, every group of picked at random butchered by 4 piglets.

Shin bone index: the mensuration of measuring calcium, phosphorus and shin bone ash content, no fat dry and bone density, shin bone volume, shin bone breaking force in the shin bone.

Stomach and enteron aisle pH: butcher the pH value of measuring stomach, jejunum, ileal contents after the end immediately with the direct insertion pH meter of pH90 type.

4. metabolic test

Just trying phase 29d 8:00 early, except that Ca 0.6%, Ca 1.0% horizontal group, all the other each levels select 3 health, near the average weight piglet, close separately respectively in the metabolic cage, receive excrement, urine entirely.Experimental period 4d.The examination pig feed intake is to pat 90% of equal feed intake in the growth test everywhere, once claims sufficient 4d material amount, freely drinks water.Add up feed intake, defecation amount and the amount of urinating every day, add 10% sulfuric acid (excrement adds 10ml by 100g, and urine adds 10ml by 100ml) in excrement and the urine respectively.Sample in time places in 0～4 ℃ of refrigerator.During due-in assembly bundle, excrement, the urine of same pig are concentrated mixing, get 1/10 kind.Excrement appearance is dried by the fire 24h down for 65 ℃ in baking oven, behind the room temperature held 6h, pulverizes and makes air-dry appearance, places-20 ℃ of refrigerators to preserve, and is to be analyzed.

Pig manure, urine samples: the calcium determinating reagent box that titration of potassium permanganate excrement calcium content, urine calcium adopt Nanjing to build up company is measured, and the phosphomolybdic acid method is measured phosphorus content in the fecaluria.

Calcium apparent digestibility (%)=(calcium is taken in the discharge rate of total amount-excrement calcium)/calcium is taken in total amount * 100

The apparent utilization rate of calcium (%)=[calcium is taken in total amount-(discharge rate of excrement calcium+urine calcium discharge rate)] * 100

Phosphorus apparent digestibility (%)=(phosphorus is taken in the discharge rate of total amount-excrement phosphorus)/phosphorus is taken in total amount * 100

The apparent utilization rate of phosphorus (%)=[phosphorus is taken in total amount-(discharge rate of excrement phosphorus+urine phosphorus discharge rate)] * 100

5. data analysis

Test data is carried out preliminary treatment with Excel.After 7d butchered, alimentary canal content pH value adopted the SAS9.0 statistical software to carry out paired sample T check.Other The data SAS9.0 statistical software carries out two factor variance analyses, and the Duncan method is carried out multiple ratio.The result representes that with average ± standard deviation P＜0.05 is thought has statistical significance.

(7) experimental result

1. in the diet Different Calcium Sources and level to the influence of piglet production performance

Annotate: mark different lowercases with line data and represent surprised significantly (P＜0.05), same letter or do not have letter representation difference not significantly (P＞0.05)

The 1:T representative is the processed group in calcium source with calcium carbonate;

The 2:N representative is the processed group in calcium source with the calcium citrate.

3:ADG: average daily gain; ADFI: average feed intake; F/G: feedstuff-meat ratio.

Visible by last table, the rising along with the diet calcium level in 0-14 days, average daily gain of piglet and feed intake all present the trend that raises and afterwards reduce earlier, and the material anharmonic ratio is irregular variation.In the calcium carbonate group, average daily gain is the highest with 0.8% group of Ca; 0.6% group of feed intake Ca is the highest, but near with Ca 0.8% winding; 0.8% group of feedstuff-meat ratio Ca is minimum.In the calcium citrate group, average daily gain is the highest with 0.8% group of Ca; 0.8% group of feed intake Ca is the highest; 0.8% group of feedstuff-meat ratio Ca is minimum.Above-mentioned each item index is difference not significantly (P＞0.05) all.Relatively, piglet average daily gain, feed intake calcium citrate Ca0.8% group are higher than other each group of calcium carbonate between calcium carbonate and calcium citrate group, but there was no significant difference (P＞0.05); 0.8% group of feedstuff-meat ratio calcium citrate Ca is lower than each group of calcium carbonate but difference not significantly (P＞0.05).Comprehensive each index of piglet production performance is thought: when 21 age in days weanling pig daily rations are the calcium source with calcium carbonate; Suitable calcium level is 0.8%; Suitable calcium level is 0.8% when being the calcium source with the calcium citrate, and comprehensively each index can know that calcium citrate is than the calcium carbonate calcium source as piglet preferably.Can improve the growth in piglets performance.

2. in the diet Different Calcium Sources and level to the influence of grice diarrhoea rate

Can know by last table 5, reach the interior grice diarrhoea index 14-28d of calcium citrate group in the calcium carbonate group and be lower than 0-14d, but there was no significant difference (P＞0.05).Along with the rising of calcium carbonate levels, the diarrhoea index presents trend of rising in the calcium carbonate group, but there was no significant difference; In the calcium citrate group diarrhoea index minimum for Ca0.6% organize but with Ca0.8% there was no significant difference (P＞0.05).Visible by data in the table, calcium citrate group grice diarrhoea index is lower than the calcium carbonate group, significantly is lower than each group (P＜0.05) of calcium carbonate in 0-14d calcium citrate group Ca0.6% group; At 14-28d, all there were significant differences (P＜0.05) for each group of calcium citrate each group and calcium carbonate.

3. in the diet Different Calcium Sources to the influence of pH value in the piglet alimentary canal

Project	Calcium carbonate Ca 0.8% level	Calcium citrate Ca 0.8% level
			Stomach pH	3.18±0.63	2.19±0.54**
Jejunum pH	6.52±0.24	6.57±0.27
			Ileum pH	7.52±0.30	7.18±0.29**

As above table can be known, calcium citrate Ca0.8% group piglet stomach and jejunum pH and calcium carbonate Ca0.8% group piglet stomach and jejunum pH have utmost point significant difference (P＜0.05), and piglet ileum pH value does not have significant difference (P＜0.05) for two groups.

4. diet Different Calcium Sources and level are to the influence of piglet blood biochemical indicator

Annotate:, represent difference extremely significantly (P＜0.01) with the different capitalizations of row labels with the different lowercase alphabet differentials of row labels different significantly (P＜0.05);

The 1:T representative is the processed group in calcium source with calcium carbonate;

The 2:N representative is the processed group in calcium source with the calcium citrate.

As above expression, serum calcium cancentration, in the calcium carbonate processed group, Ca0.8% horizontal group serum calcium cancentration is higher than other each level, but each calcium level does not have significant difference (P＞0.05).In calcium citrate was handled, the Ca0.9% horizontal group was significantly higher than other each calcium level group (P＜0.05), and all the other each levels do not have significant difference (P＞0.05).Calcium citrate and calcium carbonate compare, and calcium citrate Ca0.9% horizontal group is significantly higher than each calcium level group of calcium carbonate (P＜0.05), all the other no significant differences (P＞0.05).Serum inorganic phosphorus concentration afterwards reduces with first rising of diet calcium level.Serum inorganic phosphorus concentration raises with calcium level, presents the trend that raises and afterwards reduce earlier.In the calcium carbonate processed group, Ca0.9% horizontal group serum inorganic phosphorus concentration is significantly higher than other each level (P＜0.05), and other each group level does not have significant difference (P＞0.05).In calcium citrate was handled, Ca0.9%, Ca0.6% horizontal group were significantly higher than Ca1.0%, Ca1.1% calcium level group (P＜0.05), and other each group level does not have significant difference (P＞0.05).Comparative result showed between calcium citrate and calcium carbonate were handled, and two calcium sources are higher than other each group at Ca0.9%, but do not have significant difference (P＞0.05).Serum alkaline phosphatase activity Ca0.9% level in the calcium carbonate group is significantly higher than other each group (P＜0.05), and the Ca0.8% level is significantly higher than other each group (P＜0.05) in the calcium citrate group, and the two no significant difference (P＞0.05).Comprehensive serum biochemistry index thinks that the diet calcium level is preferable with 0.9%.

This result of the test shows, satisfies the calcium requirement of 7-8kg weanling pig optimum growh needs, and calcium carbonate is Ca0.9%, calcium citrate Ca0.8%.And find that through slaughter experiment calcium citrate has extremely significantly reduced the piglet stomach inner pH value, reduce the grice diarrhoea rate, thereby improved the piglet production performance.Find that through blood parameters calcium phosphorus utilization two calcium sources all reach the highest at Ca0.9%, but the calcium citrate group is significantly higher than the calcium carbonate group.Alkaline phosphatase activities calcium carbonate group reaches the highest when Ca0.9%, the calcium citrate group reaches the highest when Ca0.8%, shows in two the calcium source respectively when these two calcium levels, and piglet bone growth metabolism is the most active.Comprehensive The above results satisfies the daily ration calcium level of 7-8kg weanling pig optimum growh, and calcium carbonate is Ca0.9%, calcium citrate Ca0.8%.And calcium citrate can improve the production performance of piglet.Therefore, calcium citrate was than the calcium carbonate calcium source of high-quality more during piglet produced.

Two, four water citric acid calcium of the present invention and ordinary calcium carbonate (limestone powder), the calcium citrate (abbreviation ionized calcium) for preparing with the milk of lime adding citric acid feed piglet effect relatively

Select 50 of 25 age in days weanling pigs (initial body weight: 8.0 ± 0.5kg), be divided into 3 groups at random, each one group of the present invention's four water citric acid calcium, ordinary calcium carbonate and abbreviation ionized calcium; Same feed, same nursing way to manage was fed one month; Measure the calcium in the piglet blood, the calcium content of four water citric acid calcium is the highest as a result, is called for short ionized calcium and takes second place; What content was minimum is ordinary calcium carbonate, the piglet outward appearance: four water citric acid calcium hair colors of the present invention are bright, and disposition is active; The average weight of feeding one month is heavier than other two groups, than ordinary calcium carbonate feed heavy 2 kilograms, than ionized calcium feed heavy 1 kilogram.

Claims (5)

1. a calcium citrate organic feed additive contains the calcium citrate that main component is four crystallizations water, and the preparation method of the calcium citrate of four crystallizations water is following:

Raw material and parts by weight below adopting: water: 60～80; Citric acid: 16～20; Precipitated calcium carbonate 10～15; Production stage:

(1) place in the agitated reactor water boiled;

(2) get citric acid and evenly drop into agitated reactor, stir 3-10 minute, keep 60-90 ℃ to dissolving fully;

(3) get precipitated calcium carbonate, slowly evenly drop into, stir,, obtain the calcium citrate ((C of four crystallizations water to complete reaction ₆H ₅O ₇) 2Ca ₃) 4H ₂O;

(4) deposition: put into the cooling of stainless steel pond, deposition;

(5) dehydration: the product that will cool off deposition is put into centrifuge dewatering;

(6) drying: the product introducing pneumatic drier that will take off water carries out drying, and baking temperature is controlled at 120 ℃～145 ℃;

(7) screening: dry cooling back screening;

(8) check, packing.

2. calcium citrate organic feed additive according to claim 1; It is characterized in that: described precipitated calcium carbonate is that limestone calcination is generated lime and carbon dioxide; Add water digestion lime again and generate milk of lime; And then feed carbon dioxide carbonization milk of lime and generate precipitation of calcium carbonate, after dehydration, dry and pulverize and make; Perhaps carry out metathesis reaction with sodium carbonate and calcium chloride earlier and generate precipitation of calcium carbonate, make through dehydration, drying and pulverizing then.

3. calcium citrate organic feed additive according to claim 1, it is characterized in that: the grain fineness of precipitated calcium carbonate is crossed 80 mesh sieves.

4. calcium citrate organic feed additive according to claim 1, it is characterized in that: the assay of calcium citrate is: take by weighing about 0.2 gram of sample, be accurate to 0.0002 gram; Place 250 conical flasks, add 10ml water, the 2ml hydrochloric acid solution; To the sample dissolving, thin up adds triethanolamine solution 5ml to 100ml; Sodium hydroxide solution 15ml shakes up, and regulates pH greater than 13; Add calcon-carboxylic acid 0.1g, with the titration of disodium ethylene diamine tetraacetate standard titration solution, becoming pure blue to solution by aubergine is terminal point.

5. calcium citrate organic feed additive according to claim 1; It is characterized in that: the mensuration of citric acid content is to take by weighing calcium citrate sample 1g in the calcium citrate, is accurate to 0.0002g, in the 100mL beaker; Add 10mL water and dripping hydrochloric acid solution to sample dissolves; Move in the 100mL volumetric flask, add water to scale, shake up; Pipette test solution 1.00mL with pipette, place the 250mL conical flask, add water 150mL, add sulfuric acid solution 10mL and manganese sulfate 1g; In water-bath, be heated to 70 ℃,, slowly add potassium permanganate standard liquid 25.0 mL, in 70 ℃ of water-baths, place 10min constantly shaking down; With the flowing water cooling, add KI 2g, shake up, extremely faint yellow with the sodium thiosulfate standard solution titration; Add starch solution 2mL, continue titration and disappear for terminal point, through calculating citric acid content to blue.

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